WO2013180074A1 - Maintenance fluid for inkjet recording, ink set for inkjet recording, image forming method, and maintenance method - Google Patents

Maintenance fluid for inkjet recording, ink set for inkjet recording, image forming method, and maintenance method Download PDF

Info

Publication number
WO2013180074A1
WO2013180074A1 PCT/JP2013/064670 JP2013064670W WO2013180074A1 WO 2013180074 A1 WO2013180074 A1 WO 2013180074A1 JP 2013064670 W JP2013064670 W JP 2013064670W WO 2013180074 A1 WO2013180074 A1 WO 2013180074A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
group
water
mass
inkjet recording
Prior art date
Application number
PCT/JP2013/064670
Other languages
French (fr)
Japanese (ja)
Inventor
章光 配島
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2014518435A priority Critical patent/JP5823613B2/en
Priority to EP13796414.4A priority patent/EP2857204B1/en
Priority to CN201380027866.5A priority patent/CN104349901B/en
Publication of WO2013180074A1 publication Critical patent/WO2013180074A1/en
Priority to US14/552,502 priority patent/US9133359B2/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/165—Prevention or detection of nozzle clogging, e.g. cleaning, capping or moistening for nozzles
    • B41J2/16517—Cleaning of print head nozzles
    • B41J2/16552—Cleaning of print head nozzles using cleaning fluids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the present invention relates to a maintenance liquid for inkjet recording, an ink set for inkjet recording, an image forming method, and a maintenance method.
  • Recording methods using the ink jet method are widely used because, for example, high-quality images can be recorded on a wide variety of recording media by ejecting ink in droplets from a large number of nozzle holes provided in an ink jet head. It's being used.
  • a pigment is widely used for a colorant that is one of the components contained in an ink, and the pigment is used by being dispersed in a medium such as water.
  • Pigment inks containing pigments tend to thicken and gradually solidify as the solvent component in the ink evaporates. Once the pigment ink is solidified, it is difficult to be redissolved thereafter. For this reason, as the ink thickens and solidifies, it gradually accumulates at the nozzle tip of the ink jet head, resulting in narrowing or clogging of the nozzle holes, resulting in bending of the ink ejection direction or failure. This may cause problems such as causing discharge. As the ink adheres and accumulates, it becomes difficult to maintain the performance by the nozzle cap, the wipe part, and the like, and the image formability with time deteriorates.
  • the ink is more likely to be solidified and deposited as described above.
  • a cleaning liquid for cleaning ink.
  • an inkjet recording apparatus cleaning liquid containing a polyoxyalkylene monoalkyl ether having a substituent containing a polyoxyalkylene moiety as a branched chain in an alkyl chain has been disclosed (for example, a special cleaning liquid). No. 2005-146224).
  • a cleaning liquid for an inkjet apparatus containing a polyoxyalkylene monoalkyl ether containing more ethylene oxide chains than propylene oxide chains is disclosed (for example, see JP 2011-140556 A).
  • the ink refilling after washing is performed by washing the flow path through which the ink of the ink jet recording apparatus flows, not the recording head, with a cleaning liquid, and containing a specific polyoxyalkylene monoalkyl ether. It is described that there is no problem with sex.
  • an ink set having an ink containing polymer particles and a maintenance liquid containing an aromatic ring-containing organic solvent is disclosed, and a compound in which a phenyl group is bonded to an ethyleneoxy group or a propyleneoxy group is described (for example, (See JP 2010-155905 A).
  • the cleaning liquid for an ink jet recording apparatus containing polyoxyalkylene monoalkyl ether has an adverse effect when the flow path through which the ink in the ink jet recording apparatus flows rather than the recording head is cleaned by the cleaning liquid.
  • the present invention focuses on the point of preventing the dispersibility of the pigment from being lowered. Therefore, the contained component is selected from the viewpoint of stably maintaining the dispersion state of the pigment in the ink even when mixed with the ink after washing.
  • such a conventional cleaning technique is not sufficient in terms of detergency for ink solids, and further improvement of the detergency is required from the viewpoint of more stable image formation.
  • mist-like fine ink when ink is ejected, mist-like fine ink is generated and may adhere to the ejection head.
  • the adhering fine ink gradually solidifies over time, and may adhere to the head surface as a granular solid (dry ink particles).
  • dry ink particles dry ink particles
  • the maintenance liquid containing the conventional aromatic ring-containing organic solvent may not always be sufficient in terms of the solubility of the solid ink solidified by drying.
  • the present invention has been made in view of the above-described situation, and it is desired to maintain a maintenance liquid for ink jet recording excellent in solubility of ink solids solidified by drying, suppressing ejection defects such as ink ejection bending and non-ejection. It is an object of the present invention to provide an ink set for ink jet recording, an image forming method, and a maintenance method with high ink removability.
  • R 1 represents a linear or branched alkyl group having 6 to 20 carbon atoms, a linear or branched alkenyl group having 6 to 20 carbon atoms, or an aryl group.
  • m represents an integer of 3 to 14.
  • R 3 and R 5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 represents an ethylene group or a propylene group. However, R 3 and R 5 are not hydrogen atoms at the same time. x represents an integer of 1 to 4.
  • R 1 is a linear or branched alkyl group having 8 to 10 carbon atoms.
  • the total content of the water-soluble organic solvent and the humectant is 20 to 40% by mass with respect to the total amount of the maintenance liquid for inkjet recording, and the mass ratio of the water-soluble organic solvent and the humectant [water-soluble organic
  • R 1 is a linear alkyl group having 10 carbon atoms
  • m is an integer of 5 to 7
  • the HLB value of the compound represented by the general formula (I) is 11.
  • the water-soluble organic solvent is at least one selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether, ⁇ 1> to ⁇ 6>
  • the maintenance liquid for inkjet recording as described in any one of these.
  • ⁇ 8> The maintenance for inkjet recording according to any one of ⁇ 1> to ⁇ 7>, wherein the humectant is at least one selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, and triethylene glycol. liquid.
  • An ink set for inkjet recording comprising: an ink composition containing a pigment, polymer particles, and water; and the maintenance liquid for inkjet recording according to any one of ⁇ 1> to ⁇ 8>.
  • ⁇ 11> An ink application step in which the ink set for ink jet recording according to ⁇ 9> or ⁇ 10> is used, and the ink composition is applied to a recording medium by discharging the ink composition from an ink jet recording head; An ink removing step of removing the ink composition adhering to the ink jet recording head with a maintenance liquid for ink jet recording.
  • ⁇ 12> The image forming method according to ⁇ 11>, further comprising a treatment liquid application step of applying a treatment liquid containing an aggregation component that aggregates the components in the ink composition to the recording medium.
  • an ink jet recording head that discharges an ink composition for ink jet recording, and its discharge performance is maintained at or near a desired state and maintained (maintenance), in addition to recording. This includes cleaning (cleaning) the head to maintain and maintain it in a better condition.
  • the “maintenance liquid” includes a cleaning liquid for cleaning the ink composition.
  • an ink jet recording maintenance liquid excellent in solubility of ink solids solidified by drying.
  • the maintenance liquid and ink are mixed in the vicinity of the discharge port and left to dry, the agglomeration of the mixed liquid and the accompanying thickening are suppressed, and discharge defects such as ink discharge bending and non-discharge are suppressed.
  • an ink set for inkjet recording and an image forming method capable of stably forming a desired image.
  • FIG. 1 is an overall configuration diagram schematically showing an example of an ink jet recording apparatus for carrying out an image forming method of the present invention.
  • the maintenance liquid for inkjet recording of the present invention when there are a plurality of substances corresponding to the component in the composition, the amount is present in the composition unless otherwise defined. It means the total amount of the plurality of substances.
  • the maintenance liquid for inkjet recording of the present invention comprises at least a compound represented by the following general formula (I), a water-soluble organic solvent represented by the following general formula (II), a humectant, and water. Containing.
  • the maintenance liquid for inkjet recording of the present invention may further contain an organic solvent, a basic compound, other additives, and the like as necessary.
  • mist-like ink is generated during the ejection, and the ink is ejected.
  • this may be deposited including granular solids (dry ink) solidified by drying on the head.
  • cleaning is performed by applying a cleaning liquid to the ejection head, the conventional cleaning liquid is not sufficiently soluble in ink solids, and the granular ink solids remaining on the head in the process of wiping after cleaning, etc.
  • the solid solid material may enter the hole and close the discharge hole, or may be unevenly distributed near the hole and prevent ink discharge.
  • an ink solid matter is contained as compared with a conventional cleaning liquid by containing a surfactant having a specific range of HLB value and a specific structure and a water-soluble organic solvent having a specific structure having an alkyleneoxy group. Solubility is improved and excellent cleaning properties are demonstrated. For example, even when mist-like fine ink is dried and solidified, the ink is present on the head as a granular solidified product. Thus, ejection defects such as ink ejection bends and non-ejections are prevented. Thereby, it is possible to maintain a stable image forming property over a long period of time.
  • maintenance liquid for inkjet recording of the present invention
  • the maintenance liquid for inkjet recording of the present invention contains at least one compound (surfactant) represented by the following general formula (I) having an HLB value of 10.5 to 13.8. This compound penetrates the ink solid and promotes the solubility of the ink solid. Thereby, the mist-like ink generated at the time of ejection adheres to the ejection head, and the ejection failure due to the dried ink solid matter is prevented.
  • surfactant represented by the following general formula (I) having an HLB value of 10.5 to 13.8.
  • R 1 represents a linear or branched alkyl group having 6 to 20 carbon atoms, a linear or branched alkenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group.
  • m represents an integer of 3 to 14.
  • the alkyl group represented by R 1 has 6 to 20 carbon atoms, and may have a linear or branched structure.
  • Examples of the alkyl group include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, cetyl (hexadecyl) group, stearyl (octadecyl) group, nonadecyl group, icosyl group and the like.
  • a linear or branched alkyl group having 8 to 10 carbon atoms is preferable, and a linear alkyl group having 8 to 10 carbon atoms is particularly preferable.
  • the alkenyl group represented by R 1 has 6 to 20 carbon atoms, and may have a linear or branched structure.
  • alkenyl groups include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl, oleyl (octadecenyl), nonadecenyl, icocenyl and the like.
  • an alkenyl group having 8 to 10 carbon atoms is preferable.
  • the substituted or unsubstituted aryl group represented by R 1 is preferably a substituted aryl group, preferably an aryl group having 10 to 20 carbon atoms, and more preferably an aryl group having 12 to 16 carbon atoms.
  • the substituent is preferably an alkyl group, an alkenyl group, more preferably an alkyl group, and particularly preferably an alkyl group having 6 to 10 carbon atoms.
  • Preferable examples of the aryl group include nonylphenyl group and octylphenyl group.
  • M represents an integer of 3 to 14, and among them, an integer of 4 to 8 is preferable, an integer of 5 to 7 is more preferable, and an integer of 5 to 7 is particularly preferable from the viewpoint of suppressing aggregation during ink mixing.
  • m can be arbitrarily changed depending on the amount of epoxy added to the alkyl group.
  • Preferable examples of the compound represented by the general formula (I) include compounds in which R 1 is a decyl group and m is an integer of 6 to 7.
  • the HLB value of the compound represented by the general formula (I) is 10.5 to 13.8, particularly preferably in the range of 11.5 to 12.9.
  • the HLB value is less than 10.5, aggregation at the time of ink mixing is likely to occur, and ejection abnormalities are likely to occur when drying is performed over time.
  • it is larger than 13.8, the solubility of the ink solid matter is lowered, and the cleaning property is deteriorated.
  • HLB 20 ⁇ (formula weight of polyethylene oxide group) / (molecular weight) Formula 1
  • R 1 is a linear alkyl group having 8 to 10 carbon atoms, and m is from the viewpoint of aggregation suppression during ink mixing and solubility of the ink solid matter.
  • a compound having an integer of 4 to 8 and an HLB value of 11.5 to 13.4 is preferable.
  • R 1 is a linear alkyl group having 10 carbon atoms, and m is an integer of 5 to 7.
  • a compound having an HLB value of 11.5 to 12.9 is particularly preferable.
  • PEG represents “polyethylene glycol”.
  • the content of the compound represented by the general formula (I) in the maintenance liquid for ink jet recording is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the total amount of the liquid. .
  • the solubility of the ink solid matter for example, the granular ink obtained by drying and solidifying the mist-like ink
  • the content of the compound is 10% by mass or less, it is advantageous in terms of solubility in the maintenance liquid, and problems such as precipitation and turbidity are less likely to occur.
  • Two or more kinds of the compounds of the general formula (I) can be mixed and used as necessary.
  • the maintenance liquid for inkjet recording of the present invention contains at least one water-soluble organic solvent represented by the following general formula (II) together with the compound represented by the above general formula (I).
  • the solubility of the ink solid matter is further improved, and more excellent detergency is exhibited.
  • the water-soluble organic solvent represented by the following general formula (II) also has an action of dissolving the compound itself represented by the general formula (I).
  • R 3 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 represents an ethylene group or a propylene group. However, R 3 and R 5 are not hydrogen atoms at the same time. x represents an integer of 1 to 4.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R 3 and R 5 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert group. -A butyl group is mentioned.
  • Examples of the water-soluble organic solvent represented by the general formula (II) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether (DEGmME / SP value: 23.0).
  • the water-soluble organic solvent represented by the general formula (II) may be used alone or in combination of two or more.
  • the content of the water-soluble organic solvent represented by the general formula (II) in the maintenance liquid for inkjet recording is preferably 0.3 to 20% by mass, and more preferably 1 to 10% by mass. If the addition amount is less than 0.2% by mass, the effect of improving the solubility of the ink solid matter is reduced, and if it exceeds 20% by mass, the ink is likely to aggregate during ink mixing.
  • the content ratio (water-soluble organic solvent: surfactant / mass ratio) of the water-soluble organic solvent represented by the general formula (II) and the surfactant represented by the general formula (I) is 1 : 50 to 50: 1 is preferable, 1:10 to 10: 1 is more preferable, and 1: 3 to 3: 1 is still more preferable.
  • the solubility of the ink solid matter can be further improved, and the solubility of the compound represented by the general formula (I) in the maintenance liquid can also be improved. .
  • the water-soluble organic solvent can contain a compound represented by the following structural formula (1) within a range not impairing the effects of the present invention.
  • AO represents an ethyleneoxy (EO) group and / or a propyleneoxy (PO) group, and among them, a propyleneoxy group is preferable.
  • Each AO of (AO) 1 , (AO) m , and (AO) n in the structural formula may be the same or different.
  • Examples of the compound represented by the structural formula (1) include the following compounds.
  • the numerical values in parentheses indicate SP values.
  • a commercially available product may be used.
  • a polyoxypropylated glycerin ether of polypropylene glycol and glycerin
  • Sanix GP-250 Average molecular weight 250
  • GP-400 average molecular weight 400
  • GP-600 average molecular weight 600
  • the other organic solvent when an organic solvent other than the water-soluble organic solvent represented by the general formula (II) is contained, the other organic solvent has an SP value of 27.5 from the viewpoint of solubility of the ink solid matter.
  • the following organic solvents are preferable.
  • the organic solvent whose SP value is 27.5 or less 50 mass% or more with respect to the total amount of organic solvents.
  • the content of the organic solvent having an SP value of 27.5 or less is 50% by mass or more, the solubility of the fixed ink in the ejection head is further improved, and the cleaning property can be further improved.
  • the content of the organic solvent is more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the water-soluble organic solvent represented by the general formula (II) is contained in the above range.
  • the SP value is preferably 24 or less, more preferably 22 or less, from the viewpoint of improving the solubility of the ink solid matter.
  • the organic solvent include water-soluble organic solvents such as alcohols, polyols that can be used as a moisturizing agent described later, and ethers.
  • alcohols include linear or branched alkyl alcohols such as ethanol, butanol and isopropanol.
  • ethers include alkyl ethers such as diethyl ether, dibutyl ether, ethyl methyl ether, dihexyl ether, and furan.
  • lactams that can be used as moisturizers described below, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin, sulfolane and the like are also used as water-soluble organic solvents. Can be mentioned. These water-soluble organic solvents may be used alone or in combination.
  • the solubility parameter is a value represented by the square root of the molecular cohesive energy. F. Fedors, Polymer Engineering Science, 14, p. 147 to 154 (1967).
  • the total content of the organic solvent in the maintenance liquid for inkjet recording of the present invention is preferably in the range of 1 to 50% by mass with respect to the total mass of the maintenance liquid in terms of detergency.
  • the ratio of the water-soluble organic solvent represented by the general formula (II) to the total organic solvent is preferably 50% by mass or more from the viewpoint of improving the solubility of the ink solid matter.
  • the maintenance liquid for inkjet recording of the present invention preferably contains at least one humectant.
  • humectant refers to a water-soluble compound having low volatility and relatively high water retention ability.
  • humectant examples include polyols (eg, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4 -Butanediol, 1,5-pentanediol, pentaerythritol, etc.), lactams (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, etc.), etc., and water-soluble solid humectants (eg, urea, thiourea) Nitrogen compounds such as N-ethylurea, 1,6-hexanediol, 1,8-octanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, etc.
  • Diols trimethylolethane
  • Monosaccharides such as methylolpropane, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, disaccharides, oligosaccharides, And polysaccharides, and derivatives of these sugars such as reducing sugars, oxidized sugars, amino acids and thio sugars).
  • polyols are preferable, glycerin, ethylene glycol, diethylene glycol, and triethylene glycol are more preferable, and diethylene glycol is most preferable.
  • the content of the humectant in the maintenance liquid for inkjet recording is preferably in the range of 10 to 40% by mass, particularly preferably 16 to 30% by mass, based on the total amount of the maintenance liquid.
  • content of the humectant is 10% by mass or more, drying due to moisture evaporation of the maintenance liquid is suppressed.
  • content of a moisturizer is 40 mass% or less, while preventing the fall of the fluidity
  • the total content of the water-soluble organic solvent represented by the general formula (II) and the humectant is 20 to 40% by mass with respect to the total amount of the maintenance liquid, and further the water-soluble organic solvent and the humectant.
  • Is preferably 1: 1 to 1: 100, more preferably 1: 2 to 1: 9, and particularly preferably 1: 3 to 1: 5. This range is preferable from the viewpoints of the solubility of the compound of the general formula (I) of the present invention and the suppression of aggregation during drying of the ink mixture.
  • the maintenance liquid for inkjet recording of the present invention contains water as a solvent.
  • Preferable water can be pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water for the purpose of reducing ionic impurities as much as possible.
  • the ratio of water to the total mass of the maintenance liquid is preferably in the range of 50 to 80% by mass, and more preferably in the range of 60 to 70% by mass.
  • the maintenance liquid for inkjet recording of the present invention preferably contains at least one basic compound.
  • the basic compound By containing the basic compound, it is possible to provide a buffering action for preventing a pH drop due to decomposition of the contained components or the like when the maintenance liquid elapses in storage or the like.
  • the basic compound in the present invention is not particularly limited as long as it has a pH buffering ability in the pH range of the maintenance liquid, and a solvent constituting the maintenance liquid (for example, water, an organic solvent, or a mixture thereof)
  • a solvent constituting the maintenance liquid for example, water, an organic solvent, or a mixture thereof
  • a compound having a solubility of 5 mmol / L or more in the solvent is preferred.
  • the basic compound is preferably a compound having a pKa value of 6.0 to 8.5, and more preferably a pKa value of 6.8 to 8.3 in that it exhibits pH buffering capacity effectively in the pH range of the maintenance liquid. It is a compound of this.
  • the basic compound may be either an inorganic compound or an organic compound.
  • a basic organic compound is preferable because a desired pKa value is easily obtained and solubility in a maintenance solution is good.
  • the basic compound may be a monobasic compound or a polybasic compound.
  • the pKa value of the basic organic compound is the pKa value of the conjugate acid.
  • the content of the basic compound in the maintenance liquid for inkjet recording is preferably in the range of 0.01 to 10% by mass and more preferably in the range of 0.1 to 5% by mass with respect to the total amount of the maintenance liquid.
  • the content of the basic compound is 0.01% by mass or more, the pH fluctuation of the maintenance liquid is suppressed, and it is effective in preventing the occurrence of aggregation of components in the ink when mixed with the ink after washing.
  • the content is 10% by mass or less, it is advantageous in that it is difficult to deposit when the maintenance liquid is concentrated on the head surface.
  • the maintenance liquid for inkjet recording of the present invention preferably contains an antifoaming agent.
  • an antifoamer a silicone type compound, a pluronic type compound, etc. are mentioned, for example, Among these, it is more preferable that a silicone type antifoamer is included.
  • the silicone-based antifoaming agent those having a polysiloxane structure are preferable, and BYK-024 manufactured by Big Chemie Japan Co., Ltd. is particularly preferable.
  • the maintenance liquid for inkjet recording of the present invention includes, for example, an anti-fading agent, an emulsion stabilizer, a penetration accelerator, an ultraviolet absorber, a rust inhibitor, an antiseptic, an antifungal agent, pH adjusting agents, surface tension adjusting agents (nonionic surfactants, cationic surfactants, anionic surfactants, betaine surfactants, etc.), viscosity adjusting agents, silicones described in JP2011-63777A Other additives such as system compounds can be included.
  • the inkjet recording maintenance liquid of the present invention may further contain a surfactant other than the compound represented by the general formula (I) described above as a surface tension adjusting agent.
  • a surfactant include fatty acid salts, alkyl carboxylates, alkyl sulfate esters, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene.
  • Anionic surfactants such as sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid
  • Nonionic surface actives such as esters, acetylenic diol derivatives, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethyleneoxypropylene block copolymers Agents are preferred.
  • the content in the maintenance liquid is preferably 0.5 to 10% by mass with respect to the total amount of the maintenance liquid in terms of detergency.
  • the pH of the maintenance liquid in the present invention is preferably 7.0 to 9.5, more preferably 7.5 to 9.0, and particularly preferably 8.0 to 8.8.
  • the viscosity at 25 ° C. of the maintenance liquid is preferably 1 mPa ⁇ s or more and 50 mPa ⁇ s or less, more preferably 1 mPa ⁇ s or more and less than 10 mPa ⁇ s, and further preferably 2 mPa ⁇ s or more and 5 mPa ⁇ s from the viewpoint of workability. -Less than s.
  • the viscosity is a value measured at 25 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
  • the maintenance liquid of the present invention is preferably a colorless liquid containing no pigment. Moreover, there is no restriction
  • the ink set for ink-jet recording of the present invention is constituted by providing an ink composition containing a pigment, polymer particles, and water, and the above-described maintenance liquid for ink-jet recording of the present invention.
  • the ink set for inkjet recording of the present invention can be suitably configured by further providing a treatment liquid containing an aggregating component for aggregating the components in the ink composition.
  • the ink set for ink-jet recording of the present invention has a structure including the above-described maintenance liquid for ink-jet recording, so that it easily adheres to the surface of the ink discharge head because it contains pigments and polymer particles, and dissolves after drying. Since the ink that is difficult to remove, particularly the solid ink solidified by drying, is excellent in solubility, a stable image forming property is maintained for a long time. That is, for example, when mist-like ink is adhered and dried and solidified, even when granular ink is present on the head surface, the discharge hole is blocked in the process of wiping after cleaning, etc. Phenomena such as accumulation are prevented.
  • the ink composition according to the present invention contains a pigment, polymer particles, and water, and can be constituted by using additives such as urea, a derivative thereof, a wax, or a surfactant, if necessary. .
  • a conventionally well-known organic and inorganic pigment can be used.
  • polycyclic pigments such as azo lakes, azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, basic Examples include dye lakes such as dye type lakes and acid dye type lakes, organic pigments such as nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments, and inorganic pigments such as titanium oxide, iron oxide, and carbon black.
  • any pigment not described in the color index can be used as long as it can be dispersed in the aqueous phase.
  • a pigment obtained by surface-treating the above pigment with a surfactant, a polymer dispersing agent or the like, or graft carbon it is particularly preferable to use an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, or a carbon black pigment. Specific examples include pigments described in JP-A No. 2007-1000007.
  • the ink composition it is preferable that at least a part of a pigment contained as a color material is dispersed in an aqueous solvent as color material particles coated with a dispersant. Specifically, it is preferable that a part or all of the pigment is coated with a water-insoluble polymer and dispersed in the liquid. In this case, the pigment does not necessarily need to be entirely coated on the particle surface, and may be in a state where at least a part of the particle surface is coated.
  • the dispersant may be a polymer dispersant or a low molecular surfactant type dispersant.
  • a water-insoluble polymer dispersant is preferable.
  • the water-insoluble polymer is not particularly limited as long as the pigment can be dispersed, and a conventionally known water-insoluble polymer can be used.
  • As a water-insoluble polymer it can be comprised including both a hydrophobic structural unit and a hydrophilic structural unit, for example.
  • water-insoluble means that when a polymer is mixed in an aqueous medium at 25 ° C., the amount of the polymer dissolved in the aqueous medium is 10% by mass or less based on the total mass of the mixed polymers.
  • the water-insoluble polymer may be a polymer containing a repeating unit (a) represented by the following general formula (1) and a repeating unit (b) having an ionic group.
  • the polymer may further contain other structural units such as a hydrophobic repeating unit other than the repeating unit (a) and a hydrophilic repeating unit having a nonionic functional group, if necessary.
  • R 1 represents a hydrogen atom, a methyl group, or a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), and L 1 represents * —COO—, * —OCO—, * —CONR 2 —, * —O—, or a substituted or unsubstituted phenylene group, and R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • symbol * in the group represented by L 1 represents a connecting point with the main chain.
  • L 2 represents a single bond or a divalent linking group.
  • Ar represents a monovalent group derived from an aromatic ring.
  • R 1 represents a hydrogen atom, a methyl group, or a halogen atom, preferably a methyl group.
  • L 1 represents * —COO—, * —OCO—, * —CONR 2 —, * —O—, or a substituted or unsubstituted phenylene group.
  • L 1 represents a phenylene group, unsubstituted is preferred.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • L 2 represents a single bond or a divalent linking group.
  • the divalent linking group is preferably a linking group having 1 to 30 carbon atoms, more preferably a linking group having 1 to 25 carbon atoms, still more preferably a linking group having 1 to 20 carbon atoms, Particularly preferred is a linking group having 1 to 15 carbon atoms.
  • Ar represents a monovalent group derived from an aromatic ring.
  • the aromatic ring of the monovalent group represented by Ar is not particularly limited, and examples thereof include a benzene ring, a condensed aromatic ring having 8 or more carbon atoms, or an aromatic ring condensed with a hetero ring.
  • the “condensed aromatic ring having 8 or more carbon atoms” includes an aromatic ring in which at least two benzene rings are condensed, at least one aromatic ring and a condensed alicyclic hydrocarbon ring. Is an aromatic compound having 8 or more carbon atoms. Specific examples include naphthalene, anthracene, fluorene, phenanthrene, acenaphthene and the like.
  • the “aromatic ring condensed with a heterocycle” is a compound in which an aromatic compound not containing a hetero atom (preferably a benzene ring) and a cyclic compound having a hetero atom are condensed.
  • the cyclic compound having a hetero atom is preferably a 5-membered ring or a 6-membered ring.
  • a hetero atom a nitrogen atom, an oxygen atom, or a sulfur atom is preferable.
  • the cyclic compound having a hetero atom may have a plurality of hetero atoms. In this case, the heteroatoms may be the same or different from each other.
  • Specific examples of the heterocyclic ring condensed with an aromatic ring include phthalimide, acridone, carbazole, benzoxazole, and benzothiazole.
  • the monomer that forms the repeating unit (a) represented by the general formula (1) include vinyl monomers such as (meth) acrylates, (meth) acrylamides, styrenes, and vinyl esters. Can be mentioned.
  • the aromatic ring is bonded to an atom forming a part of the main chain of the water-insoluble polymer through a linking group, and the main chain of the water-insoluble polymer Since it has a structure that is not directly bonded to the atoms that form part of the structure, an appropriate distance is maintained between the hydrophobic aromatic ring and the hydrophilic structural unit, so that there is an interaction between the water-insoluble polymer and the pigment. It tends to occur and is strongly adsorbed to further improve dispersibility.
  • repeating unit (a) represented by the general formula (1) from the viewpoint of dispersion stability of the coated pigment, benzyl (meth) acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, or the general formula (1) In which Ar is a monovalent group derived from acridone or phthalimide.
  • the said repeating unit can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the repeating unit (a) represented by the general formula (1) in the polymer is preferably in the range of 5 to 25% by mass, more preferably 10 to 18% by mass with respect to the total mass of the polymer. It is a range.
  • the content is 5% by mass or more, the occurrence of image failure such as white spots tends to be remarkably suppressed, and when the content is 25% by mass or less, the polymerization in a polymerization reaction solution (for example, methyl ethyl ketone). This is preferable because there is a tendency that problems in production suitability due to a decrease in solubility do not occur.
  • the water-insoluble polymer may further have a hydrophobic repeating unit other than the repeating unit represented by the general formula (1) as a hydrophobic structural unit.
  • hydrophobic repeating units include, for example, those that do not belong to a hydrophilic structural unit (for example, have no hydrophilic functional group), such as (meth) acrylates, (meth) acrylamides, styrenes, and vinyl esters.
  • other structural units derived from vinyl monomers such as hydrophobic structural units having an aromatic ring via a linking group at the atom forming the main chain. These structural units can be used individually by 1 type or in mixture of 2 or more types.
  • Examples of the (meth) acrylates include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and hexyl (meth) acrylate.
  • alkyl esters of (meth) acrylic acid having 1 to 4 carbon atoms are preferred.
  • methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are preferable, and methyl (meth) acrylate and ethyl (meth) acrylate are particularly preferable.
  • Examples of (meth) acrylamides, styrenes, and vinyl esters include the compounds described in paragraph numbers [0063] to [0065] of JP-A No. 2001-162692.
  • the repeating unit (b) having an ionic group examples include a repeating unit derived from a monomer having an ionic group such as a carboxyl group, a sulfo group, or a phosphonate group. Examples thereof include vinyl monomers having an ionic functional group such as (meth) acrylic acid, (meth) acrylates, (meth) acrylamides, and vinyl esters.
  • the repeating unit having an ionic group can be introduced by polymerization of the corresponding monomer, but may be one in which an ionic group is introduced into the polymer chain after polymerization.
  • the repeating unit derived from acrylic acid and methacrylic acid is preferable, and it is preferable to include one or both of a structural unit derived from acrylic acid and a structural unit derived from methacrylic acid.
  • the proportion of the repeating unit (b) having an ionic group is 15% by mass or less of the total mass of the polymer, and the polymer contains at least a structural unit derived from (meth) acrylic acid as the repeating unit having an ionic group. Is preferred.
  • the content of the repeating unit (b) having an ionic group is 15% by mass or less of the total mass of the polymer, the dispersion stability is excellent.
  • the ratio of the repeating unit (b) having an ionic group is preferably 5% by mass or more and 15% by mass or less, and more preferably 7% by mass or more and 13% by mass or less from the viewpoint of dispersion stability.
  • This polymer can be stably present in an aqueous ink composition, and for example, the adhesion and deposition of aggregates in an ink jet head or the like is eased, and the removability of the adhered aggregates is excellent.
  • the hydrophobic structural unit other than the repeating unit (a) represented by the general formula (1) and the hydrophilic structural unit other than the above “repeating unit (b) having an ionic group” May further be included.
  • hydrophilic structural unit examples include a repeating unit derived from a monomer having a nonionic hydrophilic group.
  • (meth) acrylates having a hydrophilic functional group examples include (meth) acrylamides, and vinyl monomers having a hydrophilic functional group, such as vinyl esters.
  • the “hydrophilic functional group” include a hydroxyl group, an amino group, an amide group (unsubstituted with a nitrogen atom), and alkylene oxides such as polyethylene oxide and polypropylene oxide described later.
  • the monomer forming the hydrophilic repeating unit having a nonionic hydrophilic group may have a functional group capable of forming a polymer such as an ethylenically unsaturated bond and a nonionic hydrophilic functional group.
  • a functional group capable of forming a polymer such as an ethylenically unsaturated bond and a nonionic hydrophilic functional group.
  • it can be selected from known monomers.
  • Specific examples include hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylamide, aminoethyl acrylate, aminopropyl acrylate, and (meth) acrylate containing an alkylene oxide polymer.
  • the hydrophilic repeating unit having a nonionic hydrophilic group can be formed by polymerization of the corresponding monomer, but a hydrophilic functional group may be introduced into the polymer chain after polymerization.
  • the hydrophilic repeating unit having a nonionic hydrophilic group is more preferably a hydrophilic structural unit having an alkylene oxide structure.
  • the alkylene moiety of the alkylene oxide structure is preferably an alkylene having 1 to 6 carbon atoms, more preferably an alkylene having 2 to 6 carbon atoms, and particularly preferably an alkylene having 2 to 4 carbon atoms from the viewpoint of hydrophilicity.
  • the degree of polymerization of the alkylene oxide structure is preferably 1 to 120, more preferably 1 to 60, and particularly preferably 1 to 30.
  • the hydrophilic repeating unit having a nonionic hydrophilic group is a hydrophilic repeating unit containing a hydroxyl group.
  • the number of hydroxyl groups in the repeating unit is not particularly limited, and is preferably 1 to 4, more preferably 1 to 3, from the viewpoint of hydrophilicity of the water-insoluble polymer and compatibility with the solvent and other monomers during polymerization. 1-2 is particularly preferred.
  • the composition of the hydrophilic repeating unit and the hydrophobic repeating unit affects the degree of hydrophilicity and hydrophobicity of each
  • the ratio of the hydrophilic repeating unit is preferably 15% by mass or less with respect to the mass of the water-insoluble polymer.
  • a hydrophobic repeating unit is a ratio exceeding 80 mass% with respect to the whole mass of a water-insoluble polymer, and it is more preferable that it is 85 mass% or more.
  • a preferable content ratio of the hydrophilic repeating unit is more than 0% by mass and 15% by mass or less, more preferably 5 to 15% by mass, and particularly preferably 8 to 12% by mass with respect to the total mass of the water-insoluble polymer. %.
  • the content of the aromatic ring contained in the water-insoluble polymer is preferably 27% by mass or less, more preferably 25% by mass or less, and more preferably 20% by mass or less, based on the total mass of the water-insoluble polymer. More preferably it is. In particular, the content is preferably 15 to 20% by mass, and more preferably in the range of 17 to 20% by mass. When the content of the aromatic ring is within the above range, the scratch resistance is improved.
  • the acid value of the water-insoluble polymer in the present invention is preferably from 30 mgKOH / g to 100 mgKOH / g, more preferably from 30 mgKOH / g to 85 mgKOH / g from the viewpoint of pigment dispersibility and storage stability. It is preferably 50 mgKOH / g or more and 85 mgKOH / g or less.
  • the acid value is defined by the mass (mg) of KOH required to completely neutralize 1 g of the water-insoluble polymer, and is measured by the method described in JIS standard (JIS K 0070, 1992).
  • the molecular weight of the water-insoluble polymer in the present invention is preferably 30,000 or more in terms of weight average molecular weight (Mw), more preferably 30,000 to 150,000, still more preferably 30,000 to 100,000, and particularly preferably 30,000 to 100,000. 80,000.
  • the water-insoluble polymer can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization.
  • the polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.
  • the polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like.
  • the content of the pigment in the ink composition is preferably in the range of 0.1 to 15% by mass and more preferably in the range of 1 to 10% by mass with respect to the total mass of the ink composition.
  • the ink composition in the present invention contains at least one kind of polymer particles.
  • the fixability of the ink composition to the recording medium and the scratch resistance of the formed image are further improved. improves.
  • the ink is likely to adhere to and accumulate on the ejection head.
  • the ink set of the present invention is configured using the above-described maintenance liquid, ejection such as ink ejection bending or non-ejection over a long period of time. The occurrence of defects can be suppressed and good image forming properties can be maintained.
  • the polymer is “water-insoluble or sparingly water-soluble” when the resin is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C., the amount of dissolution is 15 g or less.
  • the dissolution amount is preferably 10 g or less, more preferably 5 g or less, and particularly preferably 1 g or less.
  • the dissolution amount is the dissolution amount when neutralized with sodium hydroxide or acetic acid according to the kind of the salt-forming group of the water-insoluble polymer.
  • water-insoluble polymer particles examples include thermoplastic, thermosetting or modified acrylic, epoxy, polyurethane, polyether, polyamide, unsaturated polyester, phenol, silicone, or fluorine.
  • Resins polyvinyl resins such as vinyl chloride, vinyl acetate, polyvinyl alcohol or polyvinyl butyral, polyester resins such as alkyd resins and phthalic resins, melamine resins, melamine formaldehyde resins, aminoalkyd co-condensation resins, urea resins, urea resins
  • resin particles such as amino-based materials such as copolymers or copolymers or mixtures thereof.
  • anionic acrylic resins include, for example, an acrylic monomer having an anionic group (anionic group-containing acrylic monomer) and, if necessary, other monomers copolymerizable with the anionic group-containing acrylic monomer. Obtained by polymerization in a solvent.
  • anionic group-containing acrylic monomer include acrylic monomers having one or more selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphonic acid group.
  • an acrylic monomer having a carboxyl group for example, acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid, etc.
  • acrylic acid or methacrylic acid is particularly preferable. preferable.
  • the water-insoluble polymer particles are preferably self-dispersing polymer particles from the viewpoints of ejection stability and liquid stability (particularly dispersion stability) of a system containing a pigment.
  • a self-dispersing polymer (hereinafter referred to as a self-dispersing resin) is a functional group (especially an acidic group or a salt thereof) of the polymer itself when it is dispersed by a phase inversion emulsification method in the absence of a surfactant.
  • the dispersed state means both an emulsified state (emulsion) in which a water-insoluble polymer is dispersed in an aqueous medium and a dispersed state (suspension) in which a water-insoluble polymer is dispersed in an aqueous medium. It includes the state of.
  • the self-dispersing resin is preferably a self-dispersing resin that can be in a dispersed state in which a water-insoluble polymer is dispersed in a solid state from the viewpoint of ink fixing properties when contained in the ink composition.
  • phase inversion emulsification method for example, a self-dispersing resin is dissolved or dispersed in a solvent (for example, a water-soluble organic solvent) and then poured into water as it is without adding a surfactant.
  • a solvent for example, a water-soluble organic solvent
  • examples include a method of obtaining an aqueous dispersion in an emulsified or dispersed state after stirring and mixing in a state in which a salt-forming group (for example, an acidic group) of the resin is neutralized and mixing to remove the solvent.
  • a stable emulsified or dispersed state in the self-dispersing resin is a solution in which 30 g of a water-insoluble polymer is dissolved in 70 g of an organic solvent (for example, methyl ethyl ketone), and the salt-forming group of the water-insoluble polymer can be neutralized 100%.
  • Mixing agent sodium hydroxide if the salt-forming group is anionic, acetic acid if it is cationic
  • stirring device: stirring device with stirring blades, rotation speed 200rpm, 30 minutes, 25 ° C
  • the emulsified or dispersed state is stably present at 25 ° C. for at least one week, and the occurrence of precipitation cannot be visually confirmed.
  • the stability of the emulsified or dispersed state in the self-dispersing resin can also be confirmed by an accelerated sedimentation test by centrifugation.
  • the stability of the sedimentation acceleration test by centrifugation is, for example, adjusted by adjusting the aqueous dispersion of polymer particles obtained by the above method to a solid concentration of 25% by mass, and then centrifuging at 12,000 rpm for 1 hour. It can be evaluated by measuring the solid content concentration of the supernatant after separation. If the ratio of the solid content concentration after centrifugation to the solid content concentration before centrifugation is large (a value close to 1), the sedimentation of the polymer particles by centrifugation does not occur, that is, the aqueous dispersion of polymer particles Means more stable.
  • the ratio of the solid content concentration before and after centrifugation is preferably 0.8 or more, more preferably 0.9 or more, and particularly preferably 0.95 or more.
  • the self-dispersing resin preferably has a water-soluble component content that is water-soluble when in a dispersed state of 10% by mass or less, more preferably 8% by mass or less, and 6% by mass or less. More preferably.
  • a water-soluble component content that is water-soluble when in a dispersed state of 10% by mass or less, more preferably 8% by mass or less, and 6% by mass or less. More preferably.
  • the water-soluble component is a compound contained in the self-dispersing resin and is a compound that dissolves in water when the self-dispersing resin is in a dispersed state.
  • the water-soluble component is a water-soluble compound that is by-produced or mixed in the production of the self-dispersing resin.
  • the main chain skeleton of the water-insoluble resin is not particularly limited, and examples thereof include vinyl polymers and condensation polymers (epoxy resins, polyesters, polyurethanes, polyamides, celluloses, polyethers, polyureas, polyimides, polycarbonates, etc.). Of these, vinyl polymers are particularly preferable.
  • Preferable examples of the vinyl polymer and the monomer used for producing the vinyl polymer include those described in JP-A Nos. 2001-181549 and 2002-88294.
  • a vinyl polymer in which a dissociable group is introduced at the end of a polymer chain by ionic polymerization using a compound having (or a substituent that can be derived from a dissociable group) can also be used.
  • preferred examples of the condensation polymer and the monomer used for the production of the condensation polymer include those described in JP-A-2001-247787.
  • the self-dispersing resin particles preferably include a water-insoluble polymer including a hydrophilic structural unit and a structural unit derived from an aromatic group-containing monomer or a cyclic aliphatic group-containing monomer from the viewpoint of self-dispersibility.
  • the “hydrophilic structural unit” is not particularly limited as long as it is derived from a hydrophilic group-containing monomer, and even if it is derived from one kind of hydrophilic group-containing monomer, two or more hydrophilic groups are included. It may be derived from a group-containing monomer.
  • the hydrophilic group is not particularly limited and may be a dissociable group or a nonionic hydrophilic group.
  • the hydrophilic group is preferably a dissociable group and more preferably an anionic dissociative group from the viewpoint of promoting self-dispersion and the stability of the formed emulsified or dispersed state.
  • the dissociable group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among these, a carboxyl group is preferable from the viewpoint of fixability when an ink composition is formed.
  • the hydrophilic group-containing monomer is preferably a dissociable group-containing monomer from the viewpoint of self-dispersibility and aggregability, and is preferably a dissociable group-containing monomer having a dissociable group and an ethylenically unsaturated bond.
  • the dissociable group-containing monomer include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.
  • the unsaturated carboxylic acid monomer examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxyethyl succinic acid.
  • Specific examples of the unsaturated sulfonic acid monomer and the unsaturated phosphoric acid monomer are described in paragraph numbers [0063] to [0065] of JP-A No. 2001-162692.
  • unsaturated carboxylic acid monomers are preferable, acrylic monomers are more preferable, and acrylic acid and methacrylic acid are particularly preferable.
  • the self-dispersing resin particles preferably contain a polymer having a carboxyl group, from the viewpoint of self-dispersibility and the aggregation rate at the time of contact with the processing liquid when forming an image using the processing liquid, and having a carboxyl group, More preferably, it contains a polymer having an acid value of 25 to 100 mgKOH / g. Further, the acid value is more preferably from 30 to 90 mgKOH / g, particularly preferably from 35 to 65 mgKOH / g, from the viewpoint of self-dispersibility. In particular, when the acid value is 25 mgKOH / g or more, the stability of self-dispersibility is good, and when it is 100 mgKOH / g or less, the cohesiveness is improved.
  • the aromatic group-containing monomer is not particularly limited as long as it is a compound containing an aromatic group and a polymerizable group.
  • the aromatic group may be a group derived from an aromatic hydrocarbon or a group derived from an aromatic heterocyclic ring.
  • an aromatic group derived from an aromatic hydrocarbon is preferable from the viewpoint of particle shape stability in an aqueous medium.
  • the polymerizable group may be a polycondensable polymerizable group or an addition polymerizable polymerizable group.
  • an addition polymerizable group is preferable, and a group containing an ethylenically unsaturated bond is more preferable.
  • the aromatic group-containing monomer is preferably a monomer having an aromatic group derived from an aromatic hydrocarbon and an ethylenically unsaturated bond.
  • the aromatic group-containing monomer may be used alone or in combination of two or more.
  • Examples of the aromatic group-containing monomer include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and a styrene monomer.
  • aromatic group-containing (meth) acrylate monomers are preferred from the viewpoint of the balance between the hydrophilicity and hydrophobicity of the polymer chain and the ink fixability, and include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth). At least one selected from acrylates is more preferable, and phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are more preferable.
  • “(Meth) acrylate” means acrylate or methacrylate.
  • the cycloaliphatic group-containing monomer is preferably a monomer having a cycloaliphatic group derived from a cycloaliphatic hydrocarbon and an ethylenically unsaturated bond, and a cycloaliphatic group-containing (meth) acrylate monomer (hereinafter, An alicyclic (meth) acrylate is sometimes preferred.
  • the alicyclic (meth) acrylate includes a structural site derived from (meth) acrylic acid and a structural site derived from alcohol, and the structural site derived from alcohol is unsubstituted or substituted. It has a structure containing at least one hydrogen group (cycloaliphatic group).
  • the said alicyclic hydrocarbon group may be couple
  • the alicyclic hydrocarbon group is not particularly limited as long as it contains a cyclic non-aromatic hydrocarbon group, and is a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or more polycyclic group.
  • a hydrocarbon group is mentioned.
  • the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkenyl group, a bicyclohexyl group, a norbornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group.
  • the alicyclic hydrocarbon group may further have a substituent.
  • the alicyclic hydrocarbon group may further form a condensed ring.
  • the alicyclic hydrocarbon group in the present invention preferably has 5 to 20 carbon atoms in the alicyclic hydrocarbon group portion from the viewpoint of viscosity and solubility.
  • Monocyclic (meth) acrylates include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, and cyclononyl.
  • Examples thereof include cycloalkyl (meth) acrylates having 3 to 10 carbon atoms in the cycloalkyl group such as (meth) acrylate and cyclodecyl (meth) acrylate.
  • Examples of the bicyclic (meth) acrylate include isobornyl (meth) acrylate and norbornyl (meth) acrylate.
  • Examples of the tricyclic (meth) acrylate include adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in admixture of two or more.
  • a bicyclic or tricyclic or higher (meth) acrylate is preferable, and isobornyl (meth) acrylate, adamantyl ( More preferably, it is at least one selected from (meth) acrylate and dicyclopentanyl (meth) acrylate.
  • the self-dispersing resin is preferably an acrylic resin containing a structural unit derived from a (meth) acrylate monomer, and an acrylic resin containing a structural unit derived from an aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate.
  • a resin is preferable, and further, it contains a structural unit derived from an aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate, and its content is preferably 10 to 95% by mass.
  • the stability of the self-emulsification or dispersion state is improved, and the increase in ink viscosity is further suppressed. can do.
  • the stabilization of the particle shape in the aqueous medium due to the hydrophobic interaction between the aromatic rings, and the reduction in the amount of water-soluble components due to the appropriate hydrophobicity of the particles 15 to 90% by mass More preferably, it is more preferably 15 to 80% by mass, and particularly preferably 25 to 70% by mass.
  • the self-dispersing resin includes, for example, a structural unit derived from an aromatic group-containing monomer or a cycloaliphatic group-containing monomer (preferably an alicyclic (meth) acrylate) and a structural unit derived from a dissociable group-containing monomer. Can be configured. Furthermore, other structural units may be further included as necessary.
  • the monomer forming the other structural unit is not particularly limited as long as it is a monomer copolymerizable with the aromatic group-containing monomer and the dissociable group-containing monomer.
  • an alkyl group-containing monomer for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl) (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate and other alkyl (meth) acrylates) preferable.
  • the molecular weight of the water-insoluble polymer constituting the self-dispersing resin particles is preferably from 3,000 to 200,000, more preferably from 5,000 to 150,000, and more preferably from 10,000 to 100,000. Further preferred. By setting the weight average molecular weight to 3000 or more, the amount of water-soluble components can be effectively suppressed. Moreover, self-dispersion stability can be improved by making a weight average molecular weight into 200,000 or less. The weight average molecular weight is measured by gel permeation chromatography (GPC). The details of GPC are as described above.
  • the water-insoluble polymer constituting the self-dispersing resin particles is a structural unit derived from an aromatic group-containing (meth) acrylate monomer or a cyclic aliphatic group-containing monomer (preferably an alicyclic group) from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer.
  • (Meth) acrylate) is preferably contained in a copolymerization ratio of 15 to 80% by mass of the total mass of the self-dispersing polymer particles.
  • the water-insoluble polymer is a structural unit derived from an aromatic group-containing (meth) acrylate monomer (preferably a structural unit derived from phenoxyethyl (meth) acrylate and / or benzyl (from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer).
  • Structural units derived from (meth) acrylates) or structural units derived from alicyclic (meth) acrylates preferably structural units derived from isobornyl (meth) acrylates and / or structural units derived from adamantyl (meth) acrylates and / or di).
  • water-insoluble resin forming the polymer particles include phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (50/45/5), phenoxyethyl acrylate / benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer ( 30/35/29/6), phenoxyethyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (50/44/6), phenoxyethyl acrylate / methyl methacrylate / ethyl acrylate / acrylic acid copolymer (30/55/10 / 5), benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (35/59/6), styrene / phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (10/50 35) phen
  • the insoluble resin forming the polymer particles includes a polymer synthesized in an organic solvent, and the polymer has an anionic group (for example, carboxyl group), and one of the anionic groups (for example, carboxyl group) of the polymer. Part or all of them are preferably neutralized and prepared as a polymer dispersion (dispersion) having water as a continuous phase. That is, the production of water-insoluble polymer particles includes a step of synthesizing a polymer in an organic solvent, and a dispersion step of preparing an aqueous dispersion in which at least a part of the anionic group (for example, carboxyl group) of the polymer is neutralized. It is preferable to carry out.
  • the dispersion step preferably includes the following step (1) and step (2).
  • -Step (1) Step of stirring a mixture containing a polymer (water-insoluble polymer), an organic solvent, a neutralizing agent, and an aqueous medium
  • Step (2) Step of removing the organic solvent from the mixture
  • the step (1) is preferably a treatment in which a polymer (water-insoluble polymer) is first dissolved in an organic solvent, and then a neutralizer and an aqueous medium are gradually added, mixed and stirred to obtain a dispersion.
  • a neutralizing agent and an aqueous medium are gradually added, mixed and stirred to obtain a dispersion.
  • a self-dispersing polymer having a particle size with higher storage stability without requiring strong shearing force. Particles can be obtained.
  • Dispersing machines such as a generally used mixing stirring apparatus and an ultrasonic disperser, a high-pressure homogenizer, can be used as needed.
  • the organic solvent is distilled off from the dispersion obtained in the step (1) by a conventional method such as distillation under reduced pressure, and the self-dispersing polymer particles are phase-shifted into an aqueous system.
  • An aqueous dispersion of can be obtained.
  • the organic solvent in the obtained aqueous dispersion has been substantially removed, and the amount of the organic solvent is preferably 0.2% by mass or less, more preferably 0.1% by mass or less.
  • organic solvent examples include alcohol solvents, ketone solvents, and ether solvents.
  • organic solvents exemplified in paragraph 0059 of JP 2010-188661 A can be used.
  • neutralizing agent neutralizing agents exemplified in paragraphs 0060 to 0061 of JP 2010-188661 A can be used.
  • the average particle size of the self-dispersing resin particles is preferably in the range of 10 to 400 nm in terms of volume average particle size. Further, the particle size distribution of the self-dispersing resin particles is not particularly limited, and may be either a wide particle size distribution or a monodispersed particle size distribution. Further, two or more water-insoluble particles may be mixed and used.
  • the content of the polymer particles in the ink composition is preferably 0.5 to 10% by mass and more preferably 1 to 9% by mass with respect to the total amount (mass basis) of the ink composition.
  • the content of the polymer particles is 0.5% by mass or more, the scratch resistance of the image is improved.
  • the content of the polymer particles is 10% by mass or less, it is advantageous in terms of ejection stability over a long period of time when the ink composition is prepared.
  • the ink composition in the present invention can be constituted using water. Although there is no restriction
  • the ink composition of the present invention preferably contains urea or a derivative thereof. According to urea and its derivatives, the cleaning property by wiping or the like when an ink composition containing a pigment adheres is improved. In particular, when the polymer particles are contained, the wiping property (wiping property) when dried and solidified is improved.
  • urea derivatives include compounds in which the hydrogen on the nitrogen of urea is substituted with an alkyl group or alkanol, thiourea, compounds in which the hydrogen on the nitrogen of thiourea is substituted with an alkyl group or alkanol, and the like.
  • the content of urea and its derivative in the ink composition is preferably 1.0% by mass or more and 20.0% by mass or less, and 2.0% by mass or more and 15.0% by mass with respect to the total mass of the ink composition. % Or less is more preferable.
  • the content of urea and its derivative is 1.0% by mass or more, it becomes easier to wipe off when the ink adheres, and the maintainability is improved.
  • the content of urea and its derivative is 20.0% by mass or less, it is advantageous in terms of prevention of stickiness and blocking due to moisture absorption of urea and its derivative contained in the image.
  • the ink composition in the invention may contain other components in addition to the above components, if necessary.
  • Other components include, for example, surfactants, ultraviolet absorbers, antifading agents, antifungal agents, pH adjusters, rust inhibitors, antioxidants, emulsion stabilizers, antiseptics, antifoaming agents, viscosity modifiers. And known additives such as dispersion stabilizers and chelating agents.
  • the pH of the ink composition in the present invention is not particularly limited, but the pH at 25 ° C. is pH 6.5 to from the viewpoint of preventing aggregation of the coloring material contained in the ink composition and improving the cleaning property.
  • the range of 12 is preferable, and the range of pH 7 to 10 is more preferable.
  • a pH adjuster such as the above-mentioned water-soluble basic substance can be used as necessary.
  • the ink set of the present invention is configured by providing an ink composition containing a pigment and the above-described maintenance liquid of the present invention.
  • the structure of the maintenance liquid is synonymous with the maintenance liquid of the present invention described above, and the preferred examples are also the same.
  • the maintenance liquid and ink set for ink jet recording of the present invention are used for ink jet recording. Specifically, energy is given to ink for ink jet recording, and a known image receiving material (for example, plain paper, resin) is used. (Coated paper, inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc.).
  • the image forming method of the present invention uses the ink set for ink jet recording of the present invention described above, and an ink application process for applying the ink composition to a recording medium by discharging the ink composition from the head for ink jet recording. And an ink removing step for removing the ink composition adhering to the ink jet recording head with a maintenance liquid for ink jet recording.
  • the image forming method of the present invention may further include a treatment liquid applying step of applying a treatment liquid containing an aggregating component for aggregating the components in the ink composition to the recording medium.
  • the image forming method of the present invention uses the maintenance liquid for inkjet recording of the present invention, so that it easily adheres to the surface of the ink ejection head because it contains pigments and polymer particles, and dissolves after drying. Excellent solubility of ink that is difficult to remove, especially ink solidified by drying. Therefore, stable image formability is maintained over a long period of time. As a result, in the process of wiping after cleaning, for example, the phenomenon that the discharge holes are blocked or deposits are generated in the vicinity of the discharge holes due to ink solidified, such as mist-like fine particles of ink dried and solidified, is prevented. Is done.
  • the ink composition is ejected from an ink jet recording head, whereby the ink composition is applied to the recording medium, and an image is formed on the recording medium.
  • the ink composition can be applied on the recording medium, and a desired visible image can be formed.
  • the details of the ink composition are as described above.
  • the inkjet method is not particularly limited, and is a known method, for example, a charge control method that discharges ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an electric method
  • An acoustic ink jet system that converts a signal into an acoustic beam, irradiates the ink with ink and ejects the ink using radiation pressure, and a thermal ink jet (bubble jet (registered trademark)) that heats the ink to form bubbles and uses the generated pressure. ))
  • Any method may be used.
  • an ink jet method in particular, the method described in Japanese Patent Laid-Open No.
  • Sho 54-59936 causes a sudden change in volume of the ink subjected to the action of thermal energy, and the ink is ejected from the nozzle by the action force caused by this state change.
  • Ink jet method can be used effectively.
  • the ink jet method includes a method of ejecting many low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method using is included.
  • the inkjet head used in the inkjet method may be an on-demand method or a continuous method.
  • Discharge methods include electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), and electro-thermal conversion methods (eg, thermal Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic attraction type (for example, an electric field control type, a slit jet type, etc.), a discharge type (for example, a spark jet type, etc.), and the like.
  • any discharge method may be used.
  • the ink nozzles used when recording by the inkjet method there are no particular restrictions on the ink nozzles used when recording by the inkjet method, and they can be appropriately selected according to the purpose.
  • an inkjet head As an inkjet head, a single serial head is used, and a shuttle system that performs recording while scanning the head in the width direction of the recording medium, and a line in which recording elements are arranged corresponding to the entire area of one side of the recording medium.
  • a line system using a head.
  • an image can be recorded on the entire surface of the recording medium by scanning the recording medium in a direction orthogonal to the arrangement direction of the recording elements, and a carriage system such as a carriage for scanning a short head is not necessary.
  • the recording speed can be increased as compared with the shuttle system.
  • the image forming method of the present invention can be applied to any of these, but generally, when applied to a line system that does not use a dummy jet, the effect of improving ejection accuracy and image scratch resistance is great.
  • the amount of ink droplets to be applied is preferably 1.5 to 3.0 pL, and more preferably 1.5 to 2.5 pL. More preferred.
  • the amount of ink droplets can be adjusted by appropriately selecting the ejection conditions in the ink jet method according to the ink composition to be ejected.
  • the ink composition adhered to the ink jet recording head (for example, the ink solid material solidified by drying) is discharged from the ink applying process in the ink applying process to prepare an ink jet maintenance liquid.
  • an ink jet maintenance liquid To remove.
  • the details of the configuration and preferred embodiment of the maintenance liquid used in this step are as described above.
  • a maintenance liquid is applied to the head (for example, the periphery of the head and the ink flow path; hereinafter, also referred to as “head etc.”).
  • the ink composition dissolves or swells.
  • the maintenance liquid can be applied by, for example, ejection by an ink jet method, application using a roller, spraying, and the like. For example, as described in JP 2011-73295 A, JP 2011-73339 A, etc. Using the difference, a maintenance liquid column is formed on the maintenance liquid (cleaning liquid) application unit, and when the inkjet recording head passes there, a liquid film is formed between the head and the maintenance liquid application unit, and maintenance is performed on the head. A method in which a liquid is applied is preferred.
  • the ink composition by scraping with a blade or wiping with a cloth or paper before or after applying the maintenance liquid.
  • the nozzle surface is rubbed with a wiper blade (wiping) and the ink composition is scraped off, the method of removing the ink composition by wind pressure, the liquid pressure of maintenance liquid, etc.
  • a method of wiping the ink composition with a cloth or paper is exemplified, and a method of wiping the ink composition with a cloth or paper is particularly preferable.
  • Japanese Patent Application Laid-Open No. 2010-241127 discloses a method of reducing the frequency of replacing the wiping member and making the apparatus compact.
  • the ink composition with a cloth or paper it is also possible to wipe the head surface in a wet state by directly applying a maintenance liquid to the cloth or paper.
  • This method is also preferably used because the amount of maintenance liquid to be used is smaller than the method of applying the maintenance liquid with the coating unit before wiping.
  • the material of the wiper blade is preferably elastic rubber. Specific examples of the material include butyl rubber, chloroprene rubber, ethylene propylene rubber, silicone rubber, urethane rubber, and nitrile rubber. In order to impart ink repellency to the wiper blade, a wiper blade coated with a fluorine resin or the like may be used.
  • the amount of maintenance liquid applied is not particularly limited as long as it can dissolve and swell the ink composition, but is preferably 1 to 100 g / m 2 .
  • a treatment liquid containing an aggregating component that aggregates the components in the ink composition is applied to the recording medium.
  • aggregation of pigments and the like stably dispersed in the ink composition is promoted.
  • the treatment liquid can be applied by applying a known method such as a coating method, an inkjet method, or an immersion method.
  • a coating method a known coating method using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater or the like can be used.
  • the details of the inkjet method are as described above.
  • the aggregation component is preferably at least one selected from a cationic polymer, an acidic compound, and a polyvalent metal salt from the viewpoint of image quality.
  • a polymer having a primary to tertiary amino group or a quaternary ammonium base as a cationic group is preferably used.
  • the cationic polymer includes a homopolymer of a monomer having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base (cationic monomer), or the cationic monomer and another monomer (non-cationic). That are obtained as a copolymer or a condensation polymer with a functional monomer).
  • These polymers may be used in any form of water-soluble polymer or water-dispersible latex particles.
  • poly (vinyl pyridine) salts polyalkylaminoethyl acrylate, polyalkylaminoethyl methacrylate, poly (vinyl imidazole), polyethyleneimine, polybiguanide, polyguanide, and copolymers comprising epihalohydrin derivatives and amine derivatives, and It is selected from combinations thereof.
  • the treatment liquid can be configured using an aqueous solvent (for example, water) in addition to the cationic polymer.
  • the content of the cationic polymer in the treatment liquid is preferably 5 to 95% by mass and more preferably 10 to 80% by mass with respect to the total amount of the treatment liquid in terms of the aggregation effect.
  • Examples of the acidic compound include compounds that can change the pH of the ink composition.
  • Examples of the acidic compound include a compound having a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, or a carboxyl group or a salt thereof (for example, a polyvalent metal salt).
  • a compound having a phosphate group or a carboxyl group is preferable, and a compound having a carboxyl group is more preferable.
  • the compound having a carboxyl group includes polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid. , Pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, derivatives of these compounds, or salts thereof (for example, polyvalent metal salts) Etc.
  • the pH (25 ° C.) of the treatment liquid is preferably in the range of 0.5 to 3, more preferably in the range of 0.6 to 2, from the viewpoint of the aggregation rate of the ink composition. A range of 7 to 1.5 is more preferable.
  • the pH (25 ° C.) of the ink composition is preferably 7.5 or more, and more preferably 8 or more.
  • the ink composition pH (25 ° C.) ⁇ 7.5 and the processing solution pH (25 ° C.) 0.7 to 1.5 in terms of image density, resolution, and high-speed recording. Is preferred.
  • the content of the acidic compound in the treatment liquid is preferably 5 to 95% by mass and more preferably 10 to 80% by mass with respect to the total amount of the treatment liquid in terms of the aggregation effect.
  • polyvalent metal salt examples include alkaline earth metals belonging to Group 2 of the periodic table (eg, magnesium, calcium), transition metals belonging to Group 3 of the periodic table (eg, lanthanum), and Group 13 of the periodic table. Mention may be made of salts of cations (for example aluminum) and lanthanides (for example neodymium). As the metal salt, carboxylate (formic acid, acetic acid, benzoate, etc.), nitrate, chloride, and thiocyanate are suitable.
  • calcium salts or magnesium salts of carboxylic acids (formic acid, acetic acid, benzoates, etc.), calcium salts or magnesium salts of nitric acid, calcium chloride, magnesium chloride, and calcium salts or magnesium salts of thiocyanic acid.
  • the content of the polyvalent metal salt in the treatment liquid is preferably 1 to 10% by mass, more preferably 1.5 to 7% by mass, and still more preferably 2 to 6% by mass.
  • the viscosity of the treatment liquid is preferably 1 to 30 mPa ⁇ s, more preferably 1 to 20 mPa ⁇ s, further preferably 2 to 15 mPa ⁇ s, and particularly preferably 2 to 10 mPa ⁇ s. .
  • the viscosity is a value measured at 20 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
  • the surface tension of the treatment liquid is preferably 20 to 60 mN / m, more preferably 20 to 45 mN / m, and further preferably 25 to 40 mN / m from the viewpoint of the aggregation rate of the ink composition.
  • the surface tension is a value measured at 25 ° C. using Automatic® Surface® Tensiometer® CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
  • the treatment liquid application step may be provided before or after the ink application step using the ink composition, but an embodiment provided before the ink application step is preferable.
  • a treatment liquid for aggregating components (resin particles, etc.) in the ink composition was applied in advance before applying (droplet ejection) the ink composition on the recording medium, and applied to the recording medium.
  • the ink composition is ejected in contact with the treatment liquid to form an image.
  • inkjet recording can be performed at higher speed, and an image with high density and resolution can be obtained even at high speed recording.
  • the treatment liquid on the recording medium is heated and dried after the treatment liquid is applied onto the recording medium and before the ink composition is applied.
  • ink coloring properties such as bleeding prevention are improved, and a visible image with good color density and hue can be recorded.
  • Heating and drying can be performed by a known heating means such as a heater, an air blowing means such as a dryer, or a combination of these.
  • a heating method for example, a method of applying heat with a heater or the like from the side opposite to the treatment liquid application surface of the recording medium, a method of applying warm air or hot air to the treatment liquid application surface of the recording medium, or an infrared heater was used.
  • the heating method etc. are mentioned, You may heat combining these two or more.
  • the maintenance method of the present invention applies the above-described maintenance liquid for ink jet recording of the present invention to the ink discharge head for ink jet recording to which the ink composition is adhered, and removes the ink composition on the ink discharge head for ink jet recording. Have to do.
  • the details of the configuration and preferred embodiment of the maintenance liquid are as described above.
  • the maintenance liquid for ink jet recording of the present invention since the maintenance liquid for ink jet recording of the present invention has high solubility of ink solid matter, it can be easily dissolved and removed by applying the maintenance liquid to the ink discharge head for ink jet recording, and then wiped off, etc. By this operation, it is difficult to cause adverse effects such as blockage of the discharge holes and deposition promotion in the vicinity of the discharge holes.
  • the ink composition is removed by applying a maintenance liquid to the head (for example, the periphery of the head and the ink flow path (head etc.)) in order to remove the ink composition adhering to the nozzle surface of the head.
  • a maintenance liquid for example, the periphery of the head and the ink flow path (head etc.)
  • the ink composition dissolves or swells.
  • the maintenance liquid can be applied by, for example, ejection by an inkjet method, application using a roller, spraying, or the like.
  • a maintenance liquid column is formed on a maintenance liquid (cleaning liquid) application unit using a water head difference described in Japanese Patent Application Laid-Open Nos. 2011-73295, 2011-73339, and the like.
  • a method may be used in which a liquid film is formed between the head and the maintenance liquid application unit, and the maintenance liquid is applied to the head.
  • the maintenance method can be performed by the same operation as the ink removing step in the above-described image forming method of the present invention.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC). GPC was isolated by removing the solvent from the obtained polymer, and the obtained solid content was diluted to 0.1% by mass with tetrahydrofuran, and HLC-8020 GPC (manufactured by Tosoh Corporation) was used. Measurement was carried out using three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) connected in series as a column. The conditions were as follows: the sample concentration was 0.35 mass%, the flow rate was 0.35 mL / min, the sample injection amount was 10 ⁇ L, the measurement temperature was 40 ° C., and the RI detector was used.
  • GPC gel permeation chromatography
  • the calibration curve is "Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: "F-40", “F-20”, “F-4", “F-1”, “A-5000”, “A -2500 ",” A-1000 ", and” n-propylbenzene ".
  • the acid value of the polymer was determined by the method described in JIS standard (JIS K0070: 1992).
  • Example 1 ⁇ Preparation of black ink K> -Synthesis of water-insoluble polymer dispersant P-1-
  • a water-insoluble polymer dispersant P-1 was synthesized as shown below.
  • 50 g of methyl ethyl ketone was mixed with 0.85 g of dimethyl 2,2′-azobisisobutyrate and benzyl.
  • the composition of the obtained copolymer was confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by polystyrene conversion by GPC was 44,600. Furthermore, when the acid value was calculated
  • a pigment dispersion K of resin-coated pigment particles (pigment coated with a water-insoluble polymer dispersant) was obtained.
  • the absorbance spectrum of the supernatant was measured and the pigment concentration was determined therefrom, it was 10.2% by mass. Further, the average particle size of the pigment particles dispersed in the pigment dispersion K was 130 nm.
  • step (1) a solution consisting of 1.16 g of “V-601” and 6.4 g of methyl ethyl ketone was added and stirred for 2 hours (step (1)). Subsequently, step (1) was repeated four times, and a solution consisting of 1.16 g of “V-601” and 6.4 g of methyl ethyl ketone was added and stirring was continued for 3 hours. After completion of the polymerization reaction, the temperature of the solution was lowered to 65 ° C., and 163.0 g of isopropanol was added and allowed to cool.
  • the obtained aqueous dispersion of self-dispersing polymer particles B-01 was diluted with ion-exchanged water to prepare a 25.0% dispersion, and the volume average particle size was measured by the following method. It was 0 nm.
  • the obtained aqueous dispersion of self-dispersing polymer particles is appropriately diluted to a concentration suitable for measurement (loading index is in the range of 0.1 to 10), and then ultrafine particle size distribution analyzer Nanotrac UPA-EX150 (Nikkiso (The volume average particle size of each aqueous dispersion was measured under the same measurement conditions by a dynamic light scattering method. That is, the measurement was performed under the conditions of particle permeability: transmission, particle refractive index: 1.51, particle shape: non-spherical, density: 1.2 g / cm 3 , solvent: water, cell temperature: 18 to 25 ° C.
  • a maintenance liquid was prepared by mixing components having the following composition.
  • the maintenance liquid had a viscosity of 3.1 mP ⁇ s (25 ° C.) and was adjusted to pH 8.5 (25 ° C.) with nitric acid. The viscosity was measured at 25 ° C. by VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
  • VISCOMETER TV-22 manufactured by TOKI SANGYO CO. LTD.
  • B Ink solids having a diameter of 10 ⁇ m or less are completely dissolved.
  • C Ink solids having a diameter of 7 ⁇ m or less are completely dissolved.
  • D Ink solids having a diameter of 7 ⁇ m or less remain undissolved, which may impede practical use.
  • E Ink solids having a diameter of less than 5 ⁇ m remain undissolved, which causes a practical problem.
  • Volume average particle size difference ( ⁇ ) (Volume average particle size after standing for 7 days in 30 ° C. environment) ⁇ (Volume average particle size immediately after mixing) ⁇ Evaluation criteria> A: ⁇ ⁇ 5 nm B: 5 ⁇ ⁇ 10 nm C: 10 ⁇ ⁇ 20 nm D: 20 ⁇ ⁇ 50 nm E: 50 ⁇
  • the composition of the present invention containing a compound represented by the general formula (I) having an HLB value of 10.5 to 13.8 and a water-soluble organic solvent represented by the general formula (II)
  • a maintenance liquid having excellent solubility of ink solid matter, cohesion of the ink mixture, and water solubility when drying the ink mixture was obtained.
  • the compounds represented by the general formula (I) having an HLB value of 10.5 to 13.8 a compound in which R 1 is an octyl group or a decyl group is more preferable, and in particular, a compound in which R 1 is a decyl group is more preferable. Results were obtained.
  • Example 2 Preparation of maintenance liquid>
  • the solvent in the composition, DEGmBE and the moisturizer DEG were changed to compounds of the same mass shown in Table 2 below, respectively.
  • the maintenance liquid was prepared in the same manner as in Example 13 and evaluated in the same manner as in Example 1.
  • Example 3 ⁇ Preparation of maintenance liquid>
  • the amount of addition of DEGmBE, which is a solvent in the composition, and DEG, which is a humectant was changed as shown in Table 3 below.
  • the maintenance liquid was prepared in the same manner as in Example 13 and evaluated in the same manner as in Example 1.
  • Example 4 ⁇ Preparation of colored ink> Magenta ink (M-21), cyan ink (C-21), yellow ink (Y-21), and black ink (described in paragraph number [0221] and Tables 2 to 3 of JP2011-46908A) K-21) was prepared.
  • the processing liquid was prepared by mixing components having the following composition.
  • the physical properties of the treatment liquid were a viscosity of 2.6 mPa ⁇ s, a surface tension of 41.0 mN / m, and a pH (25 ° C.) of 0.7.
  • the viscosity was measured under the condition of 20 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
  • the surface tension was measured at 25 ° C. using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
  • composition of treatment liquid ⁇ TPGmME ⁇ ⁇ ⁇ 4.8% by mass ⁇ DEGmBE (diethylene glycol monobutyl ether): 4.8% by mass ⁇
  • Malonic acid 9.0% by mass -Malic acid: 7.8% by mass ⁇ 85% by mass aqueous solution of phosphoric acid ... 6.7% by mass ⁇ 1,2,3-propanetricarboxylic acid: 2.5% by mass ⁇
  • the following water-soluble polymer 1 ... 0.6% by mass ⁇ Benzotriazole: 1.5% by mass ⁇ TSA-739 (Momentive Performance Materials Japan Defoamer) ⁇ 100ppm as the amount of silicone oil ⁇ Ion-exchanged water: Remaining amount when 100% by mass as a whole
  • a maintenance liquid was prepared by mixing components having the following composition.
  • the maintenance liquid had a viscosity of 3.1 (25 ° C.) and was adjusted to pH 8.4 with nitric acid.
  • the viscosity was measured in the same manner as in Example 1.
  • (Maintenance liquid composition) -DEGmBE (water-soluble organic solvent represented by formula (II)) ... 7.0% by mass ⁇ DEG (humectant) ... 23.0% by mass ⁇ Imidazole (pKa 7.0, basic compound) 0.5 mass% ⁇ Benzotriazole 0.1% by mass ⁇ Snowtex XS ...
  • Image formation The ink jet recording apparatus shown in FIG. 1 was prepared, and ink images were formed by ejecting the four colored inks as follows.
  • an OK top coat with a basis weight of 104 to 154 g / m 2 + (manufactured by Oji Paper Co., Ltd.) was used.
  • the image forming conditions were resolution: 1200 dpi (dot per inch) ⁇ 1200 dpi, and ejection droplet amount: equivalent to 3 pL.
  • the ink jet recording apparatus 1 shown in FIG. 1 was loaded with four colored inks prepared in advance, a treatment liquid, and a maintenance liquid.
  • 1 is an ink jet recording apparatus
  • 10 is a paper feeding unit
  • 12 is a treatment liquid application unit
  • 14 is a drawing unit
  • 16 is a drying unit
  • 18 is a fixing unit.
  • 20 is a discharge unit
  • 22 is a recording medium
  • 24 is a first intermediate conveyance unit
  • 26 is a second intermediate conveyance unit
  • 28 is a third intermediate conveyance unit
  • 30 is an intermediate conveyance body
  • 32 is a conveyance guide
  • 50 is a feeder board
  • 52 is a paper feed cylinder
  • 70 is a drawing drum
  • 72C, 72M, 72Y, and 72K are ink heads, respectively.
  • 76 is a drying drum
  • 84 is a fixing drum
  • 86 is a first fixing roller
  • 88 is a second fixing roller
  • 90 is an inline sensor
  • 92 is a paper discharge table
  • 94 is Chain delivery sprocket A DOO
  • 96 is the chain of the chain delivery 98 is the outer cover of the device.
  • the ink jet recording apparatus is activated, and the processing liquid is applied to the entire surface by the processing liquid coating device 56 on the processing liquid drum 54 (diameter 450 mm) on the recording medium 22 fed from the paper supply unit 10 (2 ⁇ m thickness). did.
  • a gravure roller was used as the treatment liquid coating device 56.
  • the recording medium 22 coated with the treatment liquid is dried by a warm air jet nozzle 58 (70 ° C. warm air (9 m 3 / min) sprayed) and an IR heater 60 (180 ° C.) to remove the solvent in the treatment liquid. Part was dried.
  • the recording medium 22 is transported to the drawing unit 14 via the first intermediate transport unit 24, and CMY (cyan, magenta, yellow) colored inks are ejected from the ejection head 72Y according to the image signal for each color solid image. , 72M, and 72C, and ejected onto the recording medium like an image.
  • the ink discharge volume was 1.4 pl in the highlight area and 3 pl (2 drops) in the high density area, and the recording density was recorded at 1200 dpi in both the main scanning and sub-scanning directions.
  • 5 pl (3 drops) can be ejected from a nozzle adjacent to the non-ejection nozzle, and a process of making it difficult to see non-ejection stripes is performed.
  • the processing liquid drum 54 and the drying drum 76 are provided separately from the drawing drum 70, even when the processing liquid is dried at a high speed, the adverse effect of the heat and wind does not reach the drawing section, and stable discharge is achieved. Was achieved.
  • a first IR heater 78 surface temperature 180 ° C.
  • a warm air ejection nozzle 80 air flow of 70 ° C. warm air (12 m 3 / min)
  • a second IR heater 82 The surface temperature was 180 ° C.
  • the drying time is about 2 seconds.
  • the recording medium 22 on which the image was formed was heat-fixed with a nip pressure of 0.30 MPa by a fixing drum 84 at 50 ° C., a first fixing roller 86 and a second fixing roller 88 at 80 ° C.
  • the first fixing roller 86 and the second fixing roller 88 a silicone rubber having a hardness of 30 ° is provided on a metal mandrel with a thickness of 6 mm, and a soft PFA coating (50 ⁇ m) is provided thereon. Thickness) was used, and a material excellent in adhesion and peelability to ink images was used.
  • the recording medium 22 was conveyed at a conveyance speed of 535 mm / s by drum conveyance by the drums 54, 70, 76, and 84. Through the above steps, an evaluation sample of a recording medium on which an image was formed was obtained.
  • the following maintenance liquid loaded in the inkjet recording apparatus is applied to the nozzle surface of the head from the maintenance liquid application unit, and then a plurality of discharge holes of the discharge head are arranged using the tresy The nozzle surface was wiped.
  • Example 5 In the preparation of the maintenance liquid “No. 48” in Example 4, No. 48 except that imidazole in the composition was removed. A maintenance liquid was prepared in the same manner as in No.48.
  • Example 6 In the preparation of the maintenance liquid of “No. 48” in Example 4, as the antifoaming agent, BYK-012, 017, 021, 022, 024, 025, 038, 094 (manufactured by BYK Japan Japan Co., Ltd.), KS- 537, KS-604, KM-72F (manufactured by Shin-Etsu Chemical Co., Ltd.), TSA-739 (manufactured by Momentive Performance Materials Japan GK), Olfin AF104 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.01% by mass was added to evaluate the maintainability and the frequency of streaks after maintenance.
  • BYK-012, 017, 021, 022, 024, 025, 038, 094 manufactured by BYK Japan Japan Co., Ltd.
  • KS- 537, KS-604, KM-72F manufactured by Shin-Etsu Chemical Co., Ltd.
  • TSA-739 manufactured by Momentive Performance Materials Japan GK
  • Olfin AF104 manufactured

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Emergency Medicine (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Detergent Compositions (AREA)

Abstract

Disclosed is a maintenance fluid for inkjet recording, containing: a compound represented by general formula (I) and having an HLB value of 10.5 to 13.8; a water-based organic solvent represented by general formula (II); a moisturizing agent; and water. In the formulas, R1 represents a straight chain or branched alkyl group with a carbon number of 6 to 20, a straight chain or branched alkenyl group with a carbon number of 6 to 20, or an aryl group. The m represents an integer from 3 to 14. R3 and R5 each independently represent either a hydrogen atom or an alkyl group with a carbon number of 1 to 4. R4 represents either an ethylene group or a propylene group. However, R3 and R5 are never hydrogen atoms at the same time. The x represents an integer from 1 to 4.

Description

インクジェット記録用メンテナンス液、インクジェット記録用インクセット、画像形成方法、及びメンテナンス方法Inkjet recording maintenance liquid, inkjet recording ink set, image forming method, and maintenance method
　本発明は、インクジェット記録用メンテナンス液、インクジェット記録用インクセット、画像形成方法、及びメンテナンス方法に関する。 The present invention relates to a maintenance liquid for inkjet recording, an ink set for inkjet recording, an image forming method, and a maintenance method.
　インクジェット法を利用した記録方法は、例えばインクジェットヘッドに設けられた多数のノズル孔からインクを液滴状に吐出することにより、多種多様な記録媒体に対して高品位の画像を記録できること等から広く利用されている。 Recording methods using the ink jet method are widely used because, for example, high-quality images can be recorded on a wide variety of recording media by ejecting ink in droplets from a large number of nozzle holes provided in an ink jet head. It's being used.
　例えば、インクの含有成分の１つである着色剤には顔料が広く用いられており、該顔料は、水等の媒質中に分散されて用いられている。
　顔料を含有する顔料インクは、インク中の溶剤成分が蒸発するに伴って増粘しやすく、次第に固化する。顔料インクは、固化してしまうとその後に再溶解し難い。そのため、インクの増粘及び固化が進行すると、インクジェットヘッドのノズル先端部等に徐々に堆積し、結果的にノズルの孔を狭めたり目詰まりを来たし、ひいてはインクの吐出方向が曲がったり、あるいは不吐出を引き起こす等の支障を来たす。インクが付着し堆積していくにつれ、ノズルキャップやワイプ部等による性能維持が困難になり、経時での画像形成性は悪化する。 For example, a pigment is widely used for a colorant that is one of the components contained in an ink, and the pigment is used by being dispersed in a medium such as water.
Pigment inks containing pigments tend to thicken and gradually solidify as the solvent component in the ink evaporates. Once the pigment ink is solidified, it is difficult to be redissolved thereafter. For this reason, as the ink thickens and solidifies, it gradually accumulates at the nozzle tip of the ink jet head, resulting in narrowing or clogging of the nozzle holes, resulting in bending of the ink ejection direction or failure. This may cause problems such as causing discharge. As the ink adheres and accumulates, it becomes difficult to maintain the performance by the nozzle cap, the wipe part, and the like, and the image formability with time deteriorates.
　さらに、例えば形成画像の擦過耐性や剥がれの防止等のために、インク中にポリマーやワックス等の高分子成分を含有する組成では、上記のようなインクの固化及び堆積がより起こりやすくなる。 Furthermore, for example, in a composition containing a polymer component such as a polymer or wax in the ink in order to prevent the formed image from being scratched or to prevent peeling, the ink is more likely to be solidified and deposited as described above.
　上記状況に関連して、インクに対する洗浄を行なうための洗浄液（いわゆるメンテナンス液）に関する検討が種々行われている。洗浄液の具体的な例として、アルキル鎖に分岐鎖としてポリオキシアルキレン部位を含む置換基を有しているポリオキシアルキレンモノアルキルエーテルを含有するインクジェット記録装置用洗浄液が開示されている（例えば、特開２００５－１４６２２４号公報参照）。また、プロピレンオキシド鎖よりエチレンオキシド鎖を多く含むポリオキシアルキレンモノアルキルエーテルを含有するインクジェット装置用洗浄液が開示されている（例えば、特開２０１１－１４０５５６号公報参照）。
　これらの文献には、洗浄液によって、記録用ヘッドではなく、インクジェット記録装置のインクが流通する流通路を洗浄すること、及び特定のポリオキシアルキレンモノアルキルエーテルを含むことで、洗浄後のインク再充填性に問題のないことが記載されている。 In connection with the above situation, various studies have been conducted on a cleaning liquid (so-called maintenance liquid) for cleaning ink. As a specific example of the cleaning liquid, an inkjet recording apparatus cleaning liquid containing a polyoxyalkylene monoalkyl ether having a substituent containing a polyoxyalkylene moiety as a branched chain in an alkyl chain has been disclosed (for example, a special cleaning liquid). No. 2005-146224). In addition, a cleaning liquid for an inkjet apparatus containing a polyoxyalkylene monoalkyl ether containing more ethylene oxide chains than propylene oxide chains is disclosed (for example, see JP 2011-140556 A).
In these documents, the ink refilling after washing is performed by washing the flow path through which the ink of the ink jet recording apparatus flows, not the recording head, with a cleaning liquid, and containing a specific polyoxyalkylene monoalkyl ether. It is described that there is no problem with sex.
　また、ポリマー粒子を含むインクと含芳香環有機溶剤を含むメンテナンス液とを有するインクセットが開示されており、フェニル基がエチレンオキシ基やプロピレンオキシ基に結合した化合物が記載されている（例えば、特開２０１０－１５５９０５号公報参照）。 Further, an ink set having an ink containing polymer particles and a maintenance liquid containing an aromatic ring-containing organic solvent is disclosed, and a compound in which a phenyl group is bonded to an ethyleneoxy group or a propyleneoxy group is described (for example, (See JP 2010-155905 A).
　上記従来の洗浄技術のうち、ポリオキシアルキレンモノアルキルエーテルを含有するインクジェット記録装置用洗浄液では、洗浄液によって、記録用ヘッドよりはむしろ、インクジェット記録装置のインクが流通する流通路を洗浄した場合の弊害、特に顔料の分散性低下を防ぐ点に着目したものである。そのため、洗浄後にインクと混合した場合にもインク中の顔料の分散状態を安定的に保つ観点から含有成分が選択されている。しかしながら、このような従来の洗浄技術では、インク固形物に対する洗浄性の点では充分でなく、より安定した画像形成性の観点からは、洗浄効果の更なる向上が必要とされる。 Among the conventional cleaning techniques described above, the cleaning liquid for an ink jet recording apparatus containing polyoxyalkylene monoalkyl ether has an adverse effect when the flow path through which the ink in the ink jet recording apparatus flows rather than the recording head is cleaned by the cleaning liquid. In particular, the present invention focuses on the point of preventing the dispersibility of the pigment from being lowered. Therefore, the contained component is selected from the viewpoint of stably maintaining the dispersion state of the pigment in the ink even when mixed with the ink after washing. However, such a conventional cleaning technique is not sufficient in terms of detergency for ink solids, and further improvement of the detergency is required from the viewpoint of more stable image formation.
　すなわち、インクを吐出した際、ミスト状の微粒のインクが発生し、これが吐出ヘッドに付着することがある。付着した微粒のインクは、経時で徐々に固化し、ヘッド面に粒状の固形物（乾燥インクの粒）として付着することがある。吐出ヘッドに洗浄液を付与して洗浄する場合、ヘッド面に付着している乾燥インクの粒（インク粒）の洗浄液による洗浄性が充分でないと、洗浄後ふき取る際に、未溶解のインク粒等の固形物が移動し、吐出孔に入り込んで閉塞したり、あるいは吐出孔付近に堆積する現象を招来する。このような現象は、洗浄後のインクの吐出に悪影響を与え、結果としてインクの吐出曲がりや不吐出等の吐出不良を引き起こすことになる。これは、特に顔料に加えてポリマー成分を含むインクの場合に顕著に現れる。 That is, when ink is ejected, mist-like fine ink is generated and may adhere to the ejection head. The adhering fine ink gradually solidifies over time, and may adhere to the head surface as a granular solid (dry ink particles). When cleaning by applying a cleaning liquid to the discharge head, if the cleaning properties of the dry ink particles (ink particles) adhering to the head surface are not sufficient, it is necessary to remove undissolved ink particles when wiping after cleaning. The solid material moves and enters into the discharge hole to be blocked, or causes a phenomenon of depositing in the vicinity of the discharge hole. Such a phenomenon adversely affects the ejection of ink after cleaning, and as a result, causes ejection defects such as ink ejection bending and non-ejection. This is particularly noticeable in the case of ink containing a polymer component in addition to the pigment.
　上記したポリオキシアルキレンモノアルキルエーテルを含有する従来の洗浄液では、流通路内に未乾燥の状態で残っているインクを、顔料分散への悪影響を抑えつつ洗浄する点ではある程度の効果は期待されるものの、上記のような乾燥により固形化したインク固形物の溶解性の点で劣る。 In the conventional cleaning liquid containing the above polyoxyalkylene monoalkyl ether, a certain degree of effect is expected in that the ink remaining in an undried state in the flow path is cleaned while suppressing adverse effects on pigment dispersion. However, it is inferior in the solubility of the solid ink solidified by drying as described above.
　また、上記従来の含芳香環有機溶剤を含むメンテナンス液では、乾燥により固形化したインク固形物の溶解性の点では、必ずしも充分でない場合がある。 Further, the maintenance liquid containing the conventional aromatic ring-containing organic solvent may not always be sufficient in terms of the solubility of the solid ink solidified by drying.
　本発明は、上記状況に鑑みなされたものであり、乾燥により固形化したインク固形物の溶解性に優れたインクジェット記録用メンテナンス液、インクの吐出曲がりや不吐出等の吐出不良を抑えて、所望の画像が安定的に形成されるインクジェット記録用インクセット及び画像形成方法、並びに、インク除去性の高いメンテナンス方法を提供することを課題とする。 The present invention has been made in view of the above-described situation, and it is desired to maintain a maintenance liquid for ink jet recording excellent in solubility of ink solids solidified by drying, suppressing ejection defects such as ink ejection bending and non-ejection. It is an object of the present invention to provide an ink set for ink jet recording, an image forming method, and a maintenance method with high ink removability.
　上記課題を達成するための具体的手段は以下の通りである。 The specific means for achieving the above-mentioned problems are as follows.
　＜１＞　ＨＬＢ値が１０．５～１３．８の下記一般式（Ｉ）で表される化合物と、下記一般式（ＩＩ）で表される水溶性有機溶剤と、保湿剤と、水とを含有するインクジェット記録用メンテナンス液。 <1> A compound represented by the following general formula (I) having an HLB value of 10.5 to 13.8, a water-soluble organic solvent represented by the following general formula (II), a humectant, and water. Contains maintenance liquid for ink jet recording.
Figure JPOXMLDOC01-appb-C000003
 
Figure JPOXMLDOC01-appb-C000003
 
　一般式（Ｉ）において、Ｒ１は、炭素数６～２０の直鎖もしくは分岐のアルキル基、炭素数６～２０の直鎖もしくは分岐のアルケニル基、又はアリール基を表す。ｍは、３～１４の整数を表す。 In the general formula (I), R 1 represents a linear or branched alkyl group having 6 to 20 carbon atoms, a linear or branched alkenyl group having 6 to 20 carbon atoms, or an aryl group. m represents an integer of 3 to 14.
Figure JPOXMLDOC01-appb-C000004
 
Figure JPOXMLDOC01-appb-C000004
 
　一般式（ＩＩ）において、Ｒ３及びＲ５は、各々独立に水素原子又は炭素数１～４のアルキル基を表し、Ｒ４はエチレン基又はプロピレン基を表す。但し、Ｒ３とＲ５が同時に水素原子であることはない。ｘは、１～４の整数を表す。
　＜２＞　一般式（Ｉ）において、Ｒ１が、炭素数８～１０の直鎖もしくは分岐のアルキル基である＜１＞に記載のインクジェット記録用メンテナンス液。
　＜３＞　水溶性有機溶剤及び保湿剤の合計の含有量が、インクジェット記録用メンテナンス液の全量に対して２０～４０質量％であり、水溶性有機溶剤と保湿剤との質量比〔水溶性有機溶剤：保湿剤〕が１：１～１：１００である＜１＞又は＜２＞に記載のインクジェット記録用メンテナンス液。
　＜４＞　更に、ｐＫａ値６．０～８．５の塩基性化合物を含有する＜１＞～＜３＞のいずれか１つに記載のインクジェット記録用メンテナンス液。 In the general formula (II), R 3 and R 5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 represents an ethylene group or a propylene group. However, R 3 and R 5 are not hydrogen atoms at the same time. x represents an integer of 1 to 4.
<2> The maintenance liquid for ink jet recording according to <1>, wherein in the general formula (I), R 1 is a linear or branched alkyl group having 8 to 10 carbon atoms.
<3> The total content of the water-soluble organic solvent and the humectant is 20 to 40% by mass with respect to the total amount of the maintenance liquid for inkjet recording, and the mass ratio of the water-soluble organic solvent and the humectant [water-soluble organic The maintenance liquid for inkjet recording according to <1> or <2>, wherein the solvent: humectant] is 1: 1 to 1: 100.
<4> The maintenance liquid for ink jet recording according to any one of <1> to <3>, further comprising a basic compound having a pKa value of 6.0 to 8.5.
　＜５＞　更に、シリコーン系消泡剤を含有する＜１＞～＜４＞のいずれか１つに記載のインクジェット記録用メンテナンス液。
　＜６＞　一般式（Ｉ）において、Ｒ１が炭素数１０の直鎖アルキル基であり、ｍが５～７の整数であり、一般式（Ｉ）で表される化合物のＨＬＢ値が１１．５～１２．９である、＜１＞～＜５＞のいずれか１つに記載のインクジェット記録用メンテナンス液。
　＜７＞　前記水溶性有機溶剤が、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル及びジプロピレングリコールモノメチルエーテルからなる群から選択される少なくとも１つである、＜１＞～＜６＞のいずれか１つに記載のインクジェット記録用メンテナンス液。
　＜８＞　前記保湿剤が、グリセリン、エチレングリコール、ジエチレングリコール及びトリエチレングリコールからなる群から選択される少なくとも１つである、＜１＞～＜７＞のいずれか１つに記載のインクジェット記録用メンテナンス液。
　＜９＞　顔料とポリマー粒子と水とを含有するインク組成物と、＜１＞～＜８＞のいずれか１つに記載のインクジェット記録用メンテナンス液と、を有するインクジェット記録用インクセット。
　＜１０＞　更に、インク組成物中の成分を凝集させる凝集成分を含有する処理液を有する＜９＞に記載のインクジェット記録用インクセット。
　＜１１＞　＜９＞又は＜１０＞に記載のインクジェット記録用インクセットが用いられ、インク組成物をインクジェット記録用ヘッドから吐出することで、インク組成物を記録媒体に付与するインク付与工程と、インクジェット記録用ヘッドに付着したインク組成物をインクジェット記録用メンテナンス液により除去するインク除去工程と、を有する画像形成方法。
　＜１２＞　更に、インク組成物中の成分を凝集させる凝集成分を含有する処理液を記録媒体に付与する処理液付与工程を有する＜１１＞に記載の画像形成方法。
　＜１３＞　インク組成物が付着したインクジェット記録用インク吐出ヘッドに対し、＜１＞～＜８＞のいずれか１つに記載のインクジェット記録用メンテナンス液を付与し、インクジェット記録用ヘッド上のインク組成物を除去することを含むメンテナンス方法。
　＜１４＞　＜１＞～＜８＞のいずれか１つに記載のインクジェット記録用メンテナンス液のメンテナンス方法における使用であって、前記メンテナンス方法は、インク組成物が付着したインクジェット記録用インク吐出ヘッドに対し、前記インクジェット記録用メンテナンス液を付与し、前記インクジェット記録用ヘッド上のインク組成物を除去することを含む、使用。 <5> The maintenance liquid for inkjet recording according to any one of <1> to <4>, further containing a silicone-based antifoaming agent.
<6> In the general formula (I), R 1 is a linear alkyl group having 10 carbon atoms, m is an integer of 5 to 7, and the HLB value of the compound represented by the general formula (I) is 11. The maintenance liquid for inkjet recording according to any one of <1> to <5>, which is 5 to 12.9.
<7> The water-soluble organic solvent is at least one selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether, <1> to <6> The maintenance liquid for inkjet recording as described in any one of these.
<8> The maintenance for inkjet recording according to any one of <1> to <7>, wherein the humectant is at least one selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, and triethylene glycol. liquid.
<9> An ink set for inkjet recording, comprising: an ink composition containing a pigment, polymer particles, and water; and the maintenance liquid for inkjet recording according to any one of <1> to <8>.
<10> The ink set for inkjet recording according to <9>, further comprising a treatment liquid containing an aggregating component that aggregates the components in the ink composition.
<11> An ink application step in which the ink set for ink jet recording according to <9> or <10> is used, and the ink composition is applied to a recording medium by discharging the ink composition from an ink jet recording head; An ink removing step of removing the ink composition adhering to the ink jet recording head with a maintenance liquid for ink jet recording.
<12> The image forming method according to <11>, further comprising a treatment liquid application step of applying a treatment liquid containing an aggregation component that aggregates the components in the ink composition to the recording medium.
<13> An ink composition on the inkjet recording head, wherein the inkjet recording maintenance liquid according to any one of <1> to <8> is applied to the inkjet recording ink discharge head to which the ink composition is adhered. A maintenance method that includes removing an object.
<14> Use of the maintenance liquid for ink jet recording according to any one of <1> to <8>, wherein the maintenance method is applied to an ink discharge head for ink jet recording to which an ink composition is attached. On the other hand, use including applying the maintenance liquid for ink jet recording and removing the ink composition on the head for ink jet recording.
　本発明における「メンテナンス」には、インクジェット記録用のインク組成物を吐出するインクジェット記録用ヘッド及びその吐出性能を所期の状態もしくはそれに近い状態に保ち、持続すること（保守）に加え、記録用ヘッドを洗浄（クリーニング）して、より良好な状態に整備、維持することが含まれる。「メンテナンス液」には、インク組成物を洗浄する洗浄液が含まれる。 In the “maintenance” in the present invention, an ink jet recording head that discharges an ink composition for ink jet recording, and its discharge performance is maintained at or near a desired state and maintained (maintenance), in addition to recording. This includes cleaning (cleaning) the head to maintain and maintain it in a better condition. The “maintenance liquid” includes a cleaning liquid for cleaning the ink composition.
　本発明によれば、乾燥により固形化したインク固形物の溶解性に優れたインクジェット記録用メンテナンス液が提供される。また、吐出口付近でメンテナンス液とインクが混ざり、それが放置され乾燥しても、混合液での凝集やそれに伴う増粘が抑制され、インクの吐出曲がりや不吐出等の吐出不良を抑えて、所望の画像が安定的に形成されるインクジェット記録用インクセット及び画像形成方法が提供される。 According to the present invention, there is provided an ink jet recording maintenance liquid excellent in solubility of ink solids solidified by drying. In addition, even if the maintenance liquid and ink are mixed in the vicinity of the discharge port and left to dry, the agglomeration of the mixed liquid and the accompanying thickening are suppressed, and discharge defects such as ink discharge bending and non-discharge are suppressed. There are provided an ink set for inkjet recording and an image forming method capable of stably forming a desired image.
本発明の画像形成方法を実施するためのインクジェット記録装置の一例を模式的に示す全体構成図である。1 is an overall configuration diagram schematically showing an example of an ink jet recording apparatus for carrying out an image forming method of the present invention.
　以下、本発明のインクジェット記録用メンテナンス液、並びにこれを用いたインクジェット記録用インクセット及び画像形成方法について詳細に説明する。
　なお、組成物中のある成分の量について言及する場合において、組成物中に当該成分に該当する物質が複数存在する場合には、特に別途定義しない限り、当該量は、組成物中に存在する当該複数の物質の合計量を意味する。 Hereinafter, the maintenance liquid for inkjet recording of the present invention, the ink set for inkjet recording using the same, and the image forming method will be described in detail.
In addition, when referring to the amount of a certain component in the composition, when there are a plurality of substances corresponding to the component in the composition, the amount is present in the composition unless otherwise defined. It means the total amount of the plurality of substances.
＜インクジェット記録用メンテナンス液＞
　本発明のインクジェット記録用メンテナンス液は、少なくとも、以下に示す一般式（Ｉ）で表される化合物と、以下に示す一般式（II）で表される水溶性有機溶剤と、保湿剤と、水とを含有する。本発明のインクジェット記録用メンテナンス液は、必要に応じて、更に、有機溶剤、塩基性化合物、その他添加剤等を含有してもよい。 <Maintenance liquid for inkjet recording>
The maintenance liquid for inkjet recording of the present invention comprises at least a compound represented by the following general formula (I), a water-soluble organic solvent represented by the following general formula (II), a humectant, and water. Containing. The maintenance liquid for inkjet recording of the present invention may further contain an organic solvent, a basic compound, other additives, and the like as necessary.
　インクジェット記録用ヘッド（以下、単に「ヘッド」又は「吐出ヘッド」ともいう）からインクを吐出して画像を形成する場合、その吐出時にミスト状の微粒のインクが発生し、この微粒のインクが吐出ヘッドに付着すると、これが、ヘッド上で乾燥により固形化した粒状の固形物（乾燥インク）を含んで堆積することがある。吐出ヘッドに洗浄液を付与して洗浄する場合、従来の洗浄液では、インク固形物に対する溶解性が充分でなく、洗浄後の拭き取り（ワイピング）等の過程でヘッド上に残存する粒状のインク固形物が移動し、例えば粒状固形物が孔に入り込んで吐出孔を閉塞したり、孔付近に偏在してインクの吐出を妨げるおそれがある。
　本発明においては、特定範囲のＨＬＢ値と特定の構造を有する界面活性剤と、アルキレンオキシ基を持つ特定構造の水溶性有機溶剤とを含有することで、従来の洗浄液に比べて、インク固形物の溶解性が高められ、優れた洗浄性を発揮する。例えばミスト状の微粒のインクが乾燥固化することでインクが粒状の固化物としてヘッド上に在る場合でも、洗浄後に拭き取る等の過程で吐出孔を閉塞したり、孔付近に堆積する等に伴って生じる、インクの吐出曲がりや不吐出等の吐出不良が防止される。これにより、長期に亘り安定した画像形成性を保持することができる。 When an image is formed by ejecting ink from an ink jet recording head (hereinafter also simply referred to as “head” or “ejection head”), mist-like ink is generated during the ejection, and the ink is ejected. When adhering to the head, this may be deposited including granular solids (dry ink) solidified by drying on the head. When cleaning is performed by applying a cleaning liquid to the ejection head, the conventional cleaning liquid is not sufficiently soluble in ink solids, and the granular ink solids remaining on the head in the process of wiping after cleaning, etc. For example, the solid solid material may enter the hole and close the discharge hole, or may be unevenly distributed near the hole and prevent ink discharge.
In the present invention, an ink solid matter is contained as compared with a conventional cleaning liquid by containing a surfactant having a specific range of HLB value and a specific structure and a water-soluble organic solvent having a specific structure having an alkyleneoxy group. Solubility is improved and excellent cleaning properties are demonstrated. For example, even when mist-like fine ink is dried and solidified, the ink is present on the head as a granular solidified product. Thus, ejection defects such as ink ejection bends and non-ejections are prevented. Thereby, it is possible to maintain a stable image forming property over a long period of time.
　以下、本発明のインクジェット記録用メンテナンス液（以下、単に「メンテナンス液」ともいう。）を構成する成分等について詳述する。 Hereinafter, components constituting the maintenance liquid for inkjet recording of the present invention (hereinafter also simply referred to as “maintenance liquid”) will be described in detail.
（一般式（Ｉ）で表される化合物）
　本発明のインクジェット記録用メンテナンス液は、ＨＬＢ値が１０．５～１３．８の下記一般式（Ｉ）で表される化合物（界面活性剤）の少なくとも一種を含有する。この化合物は、インク固形物に浸透してインク固形物の溶解性を促進する。これにより、吐出時に発生したミスト状のインクが吐出ヘッドに付着、乾燥したインク固形物による吐出不良が防止される。 (Compound represented by formula (I))
The maintenance liquid for inkjet recording of the present invention contains at least one compound (surfactant) represented by the following general formula (I) having an HLB value of 10.5 to 13.8. This compound penetrates the ink solid and promotes the solubility of the ink solid. Thereby, the mist-like ink generated at the time of ejection adheres to the ejection head, and the ejection failure due to the dried ink solid matter is prevented.
Figure JPOXMLDOC01-appb-C000005
 
Figure JPOXMLDOC01-appb-C000005
 
　上記一般式（Ｉ）において、Ｒ１は、炭素数６～２０の直鎖もしくは分岐のアルキル基、炭素数６～２０の直鎖もしくは分岐のアルケニル基、又は、置換もしくは無置換のアリール基を表す。ｍは、３～１４の整数を表す。 In the general formula (I), R 1 represents a linear or branched alkyl group having 6 to 20 carbon atoms, a linear or branched alkenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group. To express. m represents an integer of 3 to 14.
　上記Ｒ１で表されるアルキル基は、炭素数が６～２０であり、直鎖状又は分岐状のいずれの構造でもよい。アルキル基の例としては、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、セチル（ヘキサデシル）基、ステアリル（オクタデシル）基、ノナデシル基、イコシル基等が挙げられる。中でも、炭素数８～１０の直鎖状又は分岐状のアルキル基が好ましく、炭素数８～１０の直鎖のアルキル基が特に好ましい。 The alkyl group represented by R 1 has 6 to 20 carbon atoms, and may have a linear or branched structure. Examples of the alkyl group include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, cetyl (hexadecyl) group, stearyl (octadecyl) group, nonadecyl group, icosyl group and the like. Among these, a linear or branched alkyl group having 8 to 10 carbon atoms is preferable, and a linear alkyl group having 8 to 10 carbon atoms is particularly preferable.
　上記Ｒ１で表されるアルケニル基は、炭素数が６～２０であり、直鎖状又は分岐状のいずれの構造でもよい。アルケニル基の例としては、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ヘキサデセニル基、オレイル（オクタデセニル）基、ノナデセニル基、イコセニル基等が挙げられる。中でも、炭素数８～１０のアルケニル基が好ましい。 The alkenyl group represented by R 1 has 6 to 20 carbon atoms, and may have a linear or branched structure. Examples of alkenyl groups include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl, oleyl (octadecenyl), nonadecenyl, icocenyl and the like. Among them, an alkenyl group having 8 to 10 carbon atoms is preferable.
　上記Ｒ１で表される置換又は無置換のアリール基は、置換アリール基が好ましく、炭素数１０～２０のアリール基が好ましく、炭素数１２～１６のアリール基がより好ましい。アリール基が置換基を有する場合の置換基としては、アルキル基、アルケニル基等が好ましく、アルキル基が更に好ましく、炭素数６～１０のアルキル基が特に好ましい。アリール基の好ましい例としては、ノニルフェニル基、オクチルフェニル基等が挙げられる。 The substituted or unsubstituted aryl group represented by R 1 is preferably a substituted aryl group, preferably an aryl group having 10 to 20 carbon atoms, and more preferably an aryl group having 12 to 16 carbon atoms. When the aryl group has a substituent, the substituent is preferably an alkyl group, an alkenyl group, more preferably an alkyl group, and particularly preferably an alkyl group having 6 to 10 carbon atoms. Preferable examples of the aryl group include nonylphenyl group and octylphenyl group.
　また、ｍは、３～１４の整数を表し、中でも、インク混合時の凝集抑制という観点で、４～８の整数が好ましく、より好ましくは５～７の整数であり、とくに好ましくは６～７の整数である。ｍは、アルキル基に対して付加させるエポキシの仕込み量により任意に変更することができる。
　一般式（Ｉ）で表される化合物の好ましい例として、Ｒ１がデシル基であり、ｍが６～７の整数である化合物があげられる。 M represents an integer of 3 to 14, and among them, an integer of 4 to 8 is preferable, an integer of 5 to 7 is more preferable, and an integer of 5 to 7 is particularly preferable from the viewpoint of suppressing aggregation during ink mixing. Is an integer. m can be arbitrarily changed depending on the amount of epoxy added to the alkyl group.
Preferable examples of the compound represented by the general formula (I) include compounds in which R 1 is a decyl group and m is an integer of 6 to 7.
　一般式（Ｉ）で表される化合物のＨＬＢ値は、１０．５～１３．８であり、特に好ましくは１１．５～１２．９の範囲内である。ＨＬＢ値が１０．５未満であると、インク混合時の凝集が発生し易くなり、また経時過程で乾燥すると吐出異常を起こし易くなる。一方、１３．８より大きくなると、インク固形物の溶解性が低下し、洗浄性が悪化してしまう。 The HLB value of the compound represented by the general formula (I) is 10.5 to 13.8, particularly preferably in the range of 11.5 to 12.9. When the HLB value is less than 10.5, aggregation at the time of ink mixing is likely to occur, and ejection abnormalities are likely to occur when drying is performed over time. On the other hand, when it is larger than 13.8, the solubility of the ink solid matter is lowered, and the cleaning property is deteriorated.
　本発明における「ＨＬＢ値」とは、下記式１により算出される値である。
　　ＨＬＢ＝２０×（ポリエチレンオキシド基の式量）／（分子量）　・・・式１ The “HLB value” in the present invention is a value calculated by the following formula 1.
HLB = 20 × (formula weight of polyethylene oxide group) / (molecular weight) Formula 1
　上記一般式（Ｉ）で表される化合物の中では、インク混合時の凝集抑制とインク固形物の溶解性の観点から、Ｒ１が炭素数８～１０の直鎖アルキル基であり、ｍが４～８の整数であって、ＨＬＢ値が１１．５～１３．４である化合物が好ましく、更には、Ｒ１が炭素数１０の直鎖アルキル基であり、ｍが５～７の整数であって、ＨＬＢ値が１１．５～１２．９である化合物が特に好ましい。 Among the compounds represented by the general formula (I), R 1 is a linear alkyl group having 8 to 10 carbon atoms, and m is from the viewpoint of aggregation suppression during ink mixing and solubility of the ink solid matter. A compound having an integer of 4 to 8 and an HLB value of 11.5 to 13.4 is preferable. Further, R 1 is a linear alkyl group having 10 carbon atoms, and m is an integer of 5 to 7. A compound having an HLB value of 11.5 to 12.9 is particularly preferable.
　以下、上記一般式（Ｉ）で表される化合物の具体例を示す。なお、「ＰＥＧ」は「ポリエチレングリコール」を表す。 Hereinafter, specific examples of the compound represented by the general formula (I) will be shown. “PEG” represents “polyethylene glycol”.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記一般式（Ｉ）で表される化合物のインクジェット記録用メンテナンス液中における含有量としては、液全量に対して、０．１～１０質量％が好ましく、０．５～５質量％がより好ましい。一般式（Ｉ）で表される化合物の含有量が０．１質量％以上であることで、吐出ヘッド上に付着したインク固形物（例えば、ミスト状インクが乾燥固化した粒状インク）の溶解性が良好になり、洗浄性により優れる。また、該化合物の含有量が１０質量％以下であると、メンテナンス液への溶解性の点で有利であり、析出、濁り等の問題が起き難くなる。
　一般式（Ｉ）の化合物は、必要に応じて２種以上混合して用いることも可能である。 The content of the compound represented by the general formula (I) in the maintenance liquid for ink jet recording is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the total amount of the liquid. . When the content of the compound represented by the general formula (I) is 0.1% by mass or more, the solubility of the ink solid matter (for example, the granular ink obtained by drying and solidifying the mist-like ink) attached on the ejection head. Is better and has better cleaning properties. Further, when the content of the compound is 10% by mass or less, it is advantageous in terms of solubility in the maintenance liquid, and problems such as precipitation and turbidity are less likely to occur.
Two or more kinds of the compounds of the general formula (I) can be mixed and used as necessary.
（水溶性有機溶剤）
　本発明のインクジェット記録用メンテナンス液は、上記一般式（Ｉ）で表される化合物と共に、下記一般式（II）で表される水溶性有機溶剤の少なくとも一種を含有する。この水溶性有機溶剤を含有することにより、インク固形物の溶解性がより向上し、より優れた洗浄能を発揮する。また、下記一般式（II）で表される水溶性有機溶剤は、一般式（Ｉ）で表される化合物自身を溶解する作用も有する。 (Water-soluble organic solvent)
The maintenance liquid for inkjet recording of the present invention contains at least one water-soluble organic solvent represented by the following general formula (II) together with the compound represented by the above general formula (I). By containing this water-soluble organic solvent, the solubility of the ink solid matter is further improved, and more excellent detergency is exhibited. Moreover, the water-soluble organic solvent represented by the following general formula (II) also has an action of dissolving the compound itself represented by the general formula (I).
Figure JPOXMLDOC01-appb-C000007
 
Figure JPOXMLDOC01-appb-C000007
 
　上記一般式（II）において、Ｒ３及びＲ５は、各々独立に、水素原子又は炭素数１～４のアルキル基を表し、Ｒ４はエチレン基又はプロピレン基を表す。但し、Ｒ３とＲ５が同時に水素原子であることはない。ｘは、１～４の整数を表す。 In the general formula (II), R 3 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 represents an ethylene group or a propylene group. However, R 3 and R 5 are not hydrogen atoms at the same time. x represents an integer of 1 to 4.
　上記Ｒ３及びＲ５で表される炭素数１～４のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms represented by R 3 and R 5 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert group. -A butyl group is mentioned.
　上記一般式（II）で表される水溶性有機溶剤の例としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングルコールモノメチルエーテル（ＤＥＧｍＭＥ／ＳＰ値：２３．０）、ジエチレングリコールモノエチルエーテル（ＤＥＧｍＥＥ／ＳＰ値：２２．４）、ジエチレングリコールモノブチルエーテル（ＤＥＧｍＢＥ／ＳＰ値：２１．５）、トリエチレングリコールモノメチルエーテル（ＴＥＧｍＭＥ／ＳＰ値：１９．６）、トリエチレングリコールモノエチルエーテル（ＴＥＧｍＥＥ／ＳＰ値：１９．４）、トリエチレングリコールモノブチルエーテル（ＴＥＧｍＢＥ／ＳＰ値：２１．１）、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル（ＤＰＧｍＭＥ／ＳＰ値：２１．３）、トリプロピレングリコールモノメチルエーテル（ＴＰＧｍＭＥ／ＳＰ値：２１．３）、ジプロピレングリコール（ＤＰＧ／ＳＰ値：２７．２）、並びに、ｎＣ４Ｈ９Ｏ（ＡＯ）４－Ｈ（ＡＯ＝ＥＯ又はＰＯ、ＥＯ：ＰＯ［質量比］＝１：１、ＳＰ値：２０．１）、ＨＯ（ＰＯ）３－Ｈ（ＳＰ値：２４．７）等が挙げられる。上記一般式（II）で表される水溶性有機溶剤の中でも、インク固形物の溶解性と一般式（Ｉ）で表される化合物の溶解性を高める観点から、ジエチレングリコールモノブチルエーテルが最も好ましい。 Examples of the water-soluble organic solvent represented by the general formula (II) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether (DEGmME / SP value: 23.0). , Diethylene glycol monoethyl ether (DEGmEE / SP value: 22.4), diethylene glycol monobutyl ether (DEGmBE / SP value: 21.5), triethylene glycol monomethyl ether (TEGmME / SP value: 19.6), triethylene glycol mono Ethyl ether (TEGmEE / SP value: 19.4), triethylene glycol monobutyl ether (TEGmBE / SP value: 21.1), propylene glycol monomethyl ether, propylene Glycol monobutyl ether, dipropylene glycol monomethyl ether (DPGmME / SP value: 21.3), tripropylene glycol monomethyl ether (TPGmME / SP value: 21.3), dipropylene glycol (DPG / SP value: 27.2), NC 4 H 9 O (AO) 4 —H (AO = EO or PO, EO: PO [mass ratio] = 1: 1, SP value: 20.1), HO (PO) 3 —H (SP value) : 24.7) and the like. Of the water-soluble organic solvents represented by the general formula (II), diethylene glycol monobutyl ether is most preferable from the viewpoint of enhancing the solubility of the ink solid and the solubility of the compound represented by the general formula (I).
　上記一般式（II）で表される水溶性有機溶剤は、１種単独で用いるほか、２種以上を併用してもよい。
　一般式（II）で表される水溶性有機溶剤のインクジェット記録用メンテナンス液中における含有量としては、０．３～２０質量％が好ましく、１～１０質量％がより好ましい。添加量が０．２質量％未満ではインク固形物の溶解性の向上効果が小さくなり、２０質量％を超えるとインク混合時に凝集し易くなり好ましくない。 The water-soluble organic solvent represented by the general formula (II) may be used alone or in combination of two or more.
The content of the water-soluble organic solvent represented by the general formula (II) in the maintenance liquid for inkjet recording is preferably 0.3 to 20% by mass, and more preferably 1 to 10% by mass. If the addition amount is less than 0.2% by mass, the effect of improving the solubility of the ink solid matter is reduced, and if it exceeds 20% by mass, the ink is likely to aggregate during ink mixing.
　上記一般式（II）で表される水溶性有機溶剤と既述の一般式（Ｉ）で表される界面活性剤との含有比（水溶性有機溶剤：界面活性剤／質量比）は、１：５０～５０：１が好ましく、１：１０～１０：１がより好ましく、１：３～３：１が更に好ましい。含有比が上記範囲内にあることで、インク固形物の溶解性をより向上させることができ、更に一般式（Ｉ）で表される化合物のメンテナンス液中への溶解性も向上させることができる。 The content ratio (water-soluble organic solvent: surfactant / mass ratio) of the water-soluble organic solvent represented by the general formula (II) and the surfactant represented by the general formula (I) is 1 : 50 to 50: 1 is preferable, 1:10 to 10: 1 is more preferable, and 1: 3 to 3: 1 is still more preferable. When the content ratio is within the above range, the solubility of the ink solid matter can be further improved, and the solubility of the compound represented by the general formula (I) in the maintenance liquid can also be improved. .
　水溶性有機溶剤としては、上記のほか、本発明の効果を損なわない範囲で、下記構造式（1）で表される化合物を含有することができる。
Figure JPOXMLDOC01-appb-C000008
  In addition to the above, the water-soluble organic solvent can contain a compound represented by the following structural formula (1) within a range not impairing the effects of the present invention.
Figure JPOXMLDOC01-appb-C000008
　構造式（1）において、ｌ、ｍ、及びｎは、それぞれ独立に１以上の整数を表し、ｌ＋ｍ＋ｎ＝３～１５を満たす。中でも、ｌ＋ｍ＋ｎは、３以上であると洗浄性、カール抑制効果が良好になり、１５以下であると吐出性を良好に保てる。中でも、３～１２が好ましく、３～１０がより好ましい。ＡＯは、エチレンオキシ（ＥＯ）基及び／又はプロピレンオキシ（ＰＯ）基を表し、中でもプロピレンオキシ基が好ましい。構造式中の（ＡＯ）ｌ、（ＡＯ）ｍ、及び（ＡＯ）ｎの各ＡＯは、それぞれ同一でも異なってもよい。 In the structural formula (1), l, m, and n each independently represent an integer of 1 or more and satisfy l + m + n = 3 to 15. Among them, when l + m + n is 3 or more, the detergency and curl suppressing effect are good, and when it is 15 or less, the discharge property can be kept good. Among these, 3 to 12 is preferable, and 3 to 10 is more preferable. AO represents an ethyleneoxy (EO) group and / or a propyleneoxy (PO) group, and among them, a propyleneoxy group is preferable. Each AO of (AO) 1 , (AO) m , and (AO) n in the structural formula may be the same or different.
　上記構造式（1）で表される化合物の例としては、下記の化合物が挙げられる。なお、カッコ内の数値は、ＳＰ値を示す。
Figure JPOXMLDOC01-appb-C000009
  Examples of the compound represented by the structural formula (1) include the following compounds. The numerical values in parentheses indicate SP values.
Figure JPOXMLDOC01-appb-C000009
　上記構造式（1）で表される化合物としては、上市されている市販品を用いてもよく、例えば、ポリオキシプロピル化グリセリン（ポリプロピレングリコールとグリセリンとのエーテル）として、サンニックスＧＰ－２５０（平均分子量２５０）、同ＧＰ－４００（平均分子量４００）、同ＧＰ－６００（平均分子量６００）〔以上、三洋化成工業（株）製〕等を挙げることができる。 As the compound represented by the structural formula (1), a commercially available product may be used. For example, as a polyoxypropylated glycerin (ether of polypropylene glycol and glycerin), Sanix GP-250 ( Average molecular weight 250), GP-400 (average molecular weight 400), GP-600 (average molecular weight 600) [manufactured by Sanyo Chemical Industries, Ltd.].
　本発明では、上記一般式（II）で表される水溶性有機溶剤以外の他の有機溶剤を含有する場合、他の有機溶剤は、インク固形物の溶解性の観点からＳＰ値が２７．５以下の有機溶剤であることが好ましい。 In the present invention, when an organic solvent other than the water-soluble organic solvent represented by the general formula (II) is contained, the other organic solvent has an SP value of 27.5 from the viewpoint of solubility of the ink solid matter. The following organic solvents are preferable.
　本発明のメンテナンス液では、ＳＰ値が２７．５以下の有機溶剤を、全有機溶剤量に対して、５０質量％以上含有していることが好ましい。ＳＰ値が２７．５以下の有機溶剤の含有量が５０質量％以上であることで、吐出ヘッドのインク固着物の溶解性がより向上し、洗浄性をより高めることができる。中でも、該有機溶剤の含有量は、６０質量％以上がより好ましく、７０質量％以上が更に好ましく、特に好ましくは８０質量％以上である。更には、上記一般式（II）で表される水溶性有機溶剤を上記範囲で含有していることが好ましい。
　また、ＳＰ値は、インク固形物の溶解性の向上の観点から、２４以下が好ましく、２２以下が更に好ましい。 In the maintenance liquid of this invention, it is preferable to contain the organic solvent whose SP value is 27.5 or less 50 mass% or more with respect to the total amount of organic solvents. When the content of the organic solvent having an SP value of 27.5 or less is 50% by mass or more, the solubility of the fixed ink in the ejection head is further improved, and the cleaning property can be further improved. Among them, the content of the organic solvent is more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. Furthermore, it is preferable that the water-soluble organic solvent represented by the general formula (II) is contained in the above range.
The SP value is preferably 24 or less, more preferably 22 or less, from the viewpoint of improving the solubility of the ink solid matter.
　上記一般式（II）で表される水溶性有機溶剤及び上記構造式（1）で表される化合物以外の他の有機溶剤を含んでもよい。該有機溶剤としては、アルコール類、後述の保湿剤として使用可能なポリオール類、エーテル類等の水溶性有機溶剤が挙げられる。アルコール類の具体例として、エタノール、ブタノール、イソプロパノール等の直鎖又は分岐アルキルアルコール類が挙げられる。エーテル類の具体例として、ジエチルエーテル、ジブチルエーテル、エチルメチルエーテル、ジヘキシルエーテル、フラン等のアルキルエーテル類が挙げられる。また、後述の保湿剤として使用可能なラクタム類、１，３－ジメチル－２－イミダゾリジノン、ホルムアミド、アセトアミド、ジメチルスルホキシド、ソルビット、ソルビタン、アセチン、ジアセチン、トリアセチン、スルホラン等も水溶性有機溶剤として挙げることができる。
　これら水溶性有機溶剤は、１種単独であるいは複数を組み合わせて用いてもよい。 You may include organic solvents other than the water-soluble organic solvent represented by the said general formula (II), and the compound represented by the said structural formula (1). Examples of the organic solvent include water-soluble organic solvents such as alcohols, polyols that can be used as a moisturizing agent described later, and ethers. Specific examples of alcohols include linear or branched alkyl alcohols such as ethanol, butanol and isopropanol. Specific examples of ethers include alkyl ethers such as diethyl ether, dibutyl ether, ethyl methyl ether, dihexyl ether, and furan. In addition, lactams that can be used as moisturizers described below, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin, sulfolane and the like are also used as water-soluble organic solvents. Can be mentioned.
These water-soluble organic solvents may be used alone or in combination.
　上記溶解度パラメーター（ＳＰ値）とは、分子凝集エネルギーの平方根で表される値であり、Ｒ．Ｆ．Ｆｅｄｏｒｓ，Ｐｏｌｙｍｅｒ　Ｅｎｇｉｎｅｅｒｉｎｇ　Ｓｃｉｅｎｃｅ，１４，ｐ．１４７～１５４（１９６７）に記載の方法で計算される値である。 The solubility parameter (SP value) is a value represented by the square root of the molecular cohesive energy. F. Fedors, Polymer Engineering Science, 14, p. 147 to 154 (1967).
　本発明のインクジェット記録用メンテナンス液中における有機溶剤の総含有量としては、洗浄性の点で、メンテナンス液の全質量に対して、１～５０質量％の範囲が好ましい。このうち、上記一般式（II）で表される水溶性有機溶剤の全有機溶剤に対する比率が５０質量％以上であることが、インク固形物の溶解性向上の点で好ましい。 The total content of the organic solvent in the maintenance liquid for inkjet recording of the present invention is preferably in the range of 1 to 50% by mass with respect to the total mass of the maintenance liquid in terms of detergency. Among these, the ratio of the water-soluble organic solvent represented by the general formula (II) to the total organic solvent is preferably 50% by mass or more from the viewpoint of improving the solubility of the ink solid matter.
（保湿剤）
　本発明のインクジェット記録用メンテナンス液は、保湿剤の少なくとも一種を含有することが好ましい。保湿剤を含有することで、メンテナンス液の水分蒸発による乾燥を抑制し、長期放置時のメンテナンス液の組成の変質を抑制することができる。
　保湿剤とは、低揮発性で保水能力が比較的高い水溶性化合物をいう。 (Humectant)
The maintenance liquid for inkjet recording of the present invention preferably contains at least one humectant. By containing the humectant, it is possible to suppress drying of the maintenance liquid due to water evaporation, and to suppress deterioration of the composition of the maintenance liquid when left for a long time.
A humectant refers to a water-soluble compound having low volatility and relatively high water retention ability.
　保湿剤としては、例えば、ポリオール類（例：グリセリン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、ペンタエリスリトール等）、ラクタム類（例：２－ピロリドン、Ｎ－メチル－２－ピロリドン等）等、並びに水溶性の固体保湿剤（例：尿素、チオ尿素、Ｎ－エチル尿素等の窒素化合物、１，６－ヘキサンジオール、１，８－オクタンジオール、２，２－ジメチル－１，３－プロパンジオール、２，２－ジエチル－１，３－プロパンジオール等のジオール類、トリメチロールエタン、トリメチロールプロパン等、グルコース、マンノース、フルクトース、リボース、キシロース、アラビノース、ガラクトース、アルドン酸、グルシトール（ソルビット）、マルトース、セロビオース、ラクトース、スクロース、トレハロース、マルトトリオース等の単糖類、二糖類、オリゴ糖類、及び多糖類、並びにこれら糖類の還元糖、酸化糖、アミノ酸及びチオ糖等の誘導体）等が挙げられる。中でも、本発明に用いられる保湿剤としては、ポリオール類が好ましく、グリセリン、エチレングリコール、ジエチレングリコール、トリエチレングリコールがより好ましく、ジエチレングリコールが最も好ましい。 Examples of the humectant include polyols (eg, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4 -Butanediol, 1,5-pentanediol, pentaerythritol, etc.), lactams (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, etc.), etc., and water-soluble solid humectants (eg, urea, thiourea) Nitrogen compounds such as N-ethylurea, 1,6-hexanediol, 1,8-octanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, etc. Diols, trimethylolethane, Monosaccharides such as methylolpropane, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, disaccharides, oligosaccharides, And polysaccharides, and derivatives of these sugars such as reducing sugars, oxidized sugars, amino acids and thio sugars). Among them, as the humectant used in the present invention, polyols are preferable, glycerin, ethylene glycol, diethylene glycol, and triethylene glycol are more preferable, and diethylene glycol is most preferable.
　保湿剤のインクジェット記録用メンテナンス液中における含有量としては、メンテナンス液全量に対して、１０～４０質量％の範囲が好ましく、１６～３０質量％が特に好ましい。保湿剤の含有量が１０質量％以上であることで、メンテナンス液の水分蒸発による乾燥が抑制される。また、保湿剤の含有量が４０質量％以下であることで、粘度上昇による流動性の低下を防ぐと共に、良好な洗浄性を確保することができる。 The content of the humectant in the maintenance liquid for inkjet recording is preferably in the range of 10 to 40% by mass, particularly preferably 16 to 30% by mass, based on the total amount of the maintenance liquid. When the content of the humectant is 10% by mass or more, drying due to moisture evaporation of the maintenance liquid is suppressed. Moreover, while content of a moisturizer is 40 mass% or less, while preventing the fall of the fluidity | liquidity by a viscosity raise, favorable detergency can be ensured.
　一般式（II）で表される水溶性有機溶剤と保湿剤の合計の含有量がメンテナンス液全量に対して２０～４０質量％であることが特に好ましく、更に上記水溶性有機溶剤と上記保湿剤の質量比が１：１～1：１００であることが好ましく、１：２～１：９がより好ましく、１：３～１：５が特に好ましい。本発明の一般式（Ｉ）の化合物の溶解性、インク混合液の乾燥時の凝集抑制の観点でこの範囲が好ましい。 It is particularly preferable that the total content of the water-soluble organic solvent represented by the general formula (II) and the humectant is 20 to 40% by mass with respect to the total amount of the maintenance liquid, and further the water-soluble organic solvent and the humectant. Is preferably 1: 1 to 1: 100, more preferably 1: 2 to 1: 9, and particularly preferably 1: 3 to 1: 5. This range is preferable from the viewpoints of the solubility of the compound of the general formula (I) of the present invention and the suppression of aggregation during drying of the ink mixture.
（水）
　本発明のインクジェット記録用メンテナンス液は、溶剤として水を含有する。
　好ましい水は、イオン性の不純物を極力低減することを目的として、イオン交換水、限外濾過水、逆浸透水、蒸留水等の純水、又は超純水を用いることができる。
　水のメンテナンス液の全質量に占める割合は、５０～８０質量％の範囲が好ましく、６０～７０質量％の範囲が更に好ましい。 (water)
The maintenance liquid for inkjet recording of the present invention contains water as a solvent.
Preferable water can be pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water for the purpose of reducing ionic impurities as much as possible.
The ratio of water to the total mass of the maintenance liquid is preferably in the range of 50 to 80% by mass, and more preferably in the range of 60 to 70% by mass.
（塩基性化合物）
　本発明のインクジェット記録用メンテナンス液は、塩基性化合物の少なくとも一種を含有することが好ましい。塩基性化合物を含有することで、メンテナンス液が保管等で経時した場合に、含有成分の分解等でｐＨ低下するのを防ぐための緩衝作用を持たせることができる。 (Basic compound)
The maintenance liquid for inkjet recording of the present invention preferably contains at least one basic compound. By containing the basic compound, it is possible to provide a buffering action for preventing a pH drop due to decomposition of the contained components or the like when the maintenance liquid elapses in storage or the like.
　本発明における塩基性化合物は、メンテナンス液のｐＨ領域においてｐＨ緩衝能を有する化合物であれば、特に限定されるものではなく、メンテナンス液を構成する溶剤（例えば、水、有機溶剤、又はこれらの混合溶剤）に５ｍｍｏｌ／Ｌ以上の溶解度を有する化合物が好ましい。 The basic compound in the present invention is not particularly limited as long as it has a pH buffering ability in the pH range of the maintenance liquid, and a solvent constituting the maintenance liquid (for example, water, an organic solvent, or a mixture thereof) A compound having a solubility of 5 mmol / L or more in the solvent is preferred.
　塩基性化合物としては、メンテナンス液のｐＨ領域で有効にｐＨ緩衝能を示す点で、ｐＫａ値が６．０～８．５の化合物が好ましく、より好ましくはｐＫａ値が６．８～８．３の化合物である。 The basic compound is preferably a compound having a pKa value of 6.0 to 8.5, and more preferably a pKa value of 6.8 to 8.3 in that it exhibits pH buffering capacity effectively in the pH range of the maintenance liquid. It is a compound of this.
　塩基性化合物は、無機化合物及び有機化合物のいずれでもよい。所望のｐＫａ値を得やすいこと、メンテナンス溶液への溶解性が良好である点から、塩基性化合物としては、塩基性有機化合物が好ましい。また、塩基性化合物は、一塩基化合物であっても多塩基化合物であってもよい。なお、塩基性有機化合物のｐＫａ値は、共役酸のｐＫａ値である。 The basic compound may be either an inorganic compound or an organic compound. As the basic compound, a basic organic compound is preferable because a desired pKa value is easily obtained and solubility in a maintenance solution is good. The basic compound may be a monobasic compound or a polybasic compound. The pKa value of the basic organic compound is the pKa value of the conjugate acid.
　塩基性化合物としては、例えば、下記具体例が挙げられる。
　・カコジル酸（ｐＫａ：６．２）
　・２，２－ビス（ヒドロキシメチル）－２，２’，２”－ニトリロトリエタノール（ｐＫａ：６．５）
　・ピペラジン－Ｎ，Ｎ’－ビス－（２－エタン硫酸）（ｐＫａ：６．８）
　・リン酸（ｐＫａ２：６．８６）
　・イミダゾール（ｐＫａ：７．０）
　・Ｎ’－２－ヒドロキシエチルピペラジン－Ｎ’，２－エタン硫酸（ｐＫａ：７．６）
　・Ｎ－メチルモルホリン（ｐＫａ：７．８）
　・トリエタノールアミン（ｐＫａ：７．８）
　・ヒドラジン（ｐＫａ：８．１１）
　・トリスヒドロキシメチルアミノメタン（ｐＫａ：８．３） As a basic compound, the following specific example is mentioned, for example.
・ Cacodylic acid (pKa: 6.2)
2,2-bis (hydroxymethyl) -2,2 ′, 2 ″ -nitrilotriethanol (pKa: 6.5)
Piperazine-N, N′-bis- (2-ethanesulfuric acid) (pKa: 6.8)
Phosphoric acid (pKa2: 6.86)
-Imidazole (pKa: 7.0)
N′-2-hydroxyethylpiperazine-N ′, 2-ethanesulfuric acid (pKa: 7.6)
N-methylmorpholine (pKa: 7.8)
Triethanolamine (pKa: 7.8)
・ Hydrazine (pKa: 8.11)
Trishydroxymethylaminomethane (pKa: 8.3)
　塩基性化合物のインクジェット記録用メンテナンス液中における含有量としては、メンテナンス液全量に対して、０．０１～１０質量％の範囲が好ましく、０．１～５質量％の範囲がより好ましい。塩基性化合物の含有量が０．０１質量％以上であると、メンテナンス液のｐＨ変動が抑えられ、洗浄後にインクと混合した場合にインク中の成分の凝集等の発生防止に効果的である。含有量が１０質量％以下であると、ヘッド面でメンテナンス液が濃縮されたときに析出し難いという点で有利である。 The content of the basic compound in the maintenance liquid for inkjet recording is preferably in the range of 0.01 to 10% by mass and more preferably in the range of 0.1 to 5% by mass with respect to the total amount of the maintenance liquid. When the content of the basic compound is 0.01% by mass or more, the pH fluctuation of the maintenance liquid is suppressed, and it is effective in preventing the occurrence of aggregation of components in the ink when mixed with the ink after washing. When the content is 10% by mass or less, it is advantageous in that it is difficult to deposit when the maintenance liquid is concentrated on the head surface.
（消泡剤）
　本発明のインクジェット記録用メンテナンス液は、消泡剤を含むことが好ましい。消泡剤としては、例えばシリコーン系化合物、プルロニック系化合物等が挙げられ、これらの中でも、シリコーン系消泡剤を含むことがより好ましい。シリコーン系消泡剤としては、ポリシロキサン構造を有しているものが好ましく、ビックケミー・ジャパン（株）製のＢＹＫ－０２４が特に好ましい。 (Defoamer)
The maintenance liquid for inkjet recording of the present invention preferably contains an antifoaming agent. As an antifoamer, a silicone type compound, a pluronic type compound, etc. are mentioned, for example, Among these, it is more preferable that a silicone type antifoamer is included. As the silicone-based antifoaming agent, those having a polysiloxane structure are preferable, and BYK-024 manufactured by Big Chemie Japan Co., Ltd. is particularly preferable.
（その他添加剤）
　本発明のインクジェット記録用メンテナンス液は、上記の成分に加え、必要に応じて、例えば、褪色防止剤、乳化安定剤、浸透促進剤、紫外線吸収剤、防錆剤、防腐剤、防黴剤、ｐＨ調整剤、表面張力調整剤（ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、ベタイン系界面活性剤等）、粘度調整剤、特開２０１１－６３７７７号公報に記載のシリコーン系化合物等のその他の添加剤を含むことができる。 (Other additives)
In addition to the above-described components, the maintenance liquid for inkjet recording of the present invention includes, for example, an anti-fading agent, an emulsion stabilizer, a penetration accelerator, an ultraviolet absorber, a rust inhibitor, an antiseptic, an antifungal agent, pH adjusting agents, surface tension adjusting agents (nonionic surfactants, cationic surfactants, anionic surfactants, betaine surfactants, etc.), viscosity adjusting agents, silicones described in JP2011-63777A Other additives such as system compounds can be included.
　本発明のインクジェット記録用メンテナンス液は、表面張力調整剤として、既述の一般式（Ｉ）で表される化合物以外の界面活性剤を更に含んでもよい。
　該界面活性剤としては、例えば、脂肪酸塩、アルキルカルボン酸塩、アルキル硫酸エステル塩、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ジアルキルスルホコハク酸塩、アルキルリン酸エステル塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキル硫酸エステル塩等のアニオン系界面活性剤や、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、アセチレンジオール誘導体、ポリオキシエチレンアルキルアミン、グリセリン脂肪酸エステル、オキシエチレンオキシプロピレンブロックコポリマー等のノニオン系界面活性剤が好ましい。このような界面活性剤を含む場合、そのメンテナンス液中における含有量は、洗浄性の点で、メンテナンス液全量に対して０．５～１０質量％が好ましい。 The inkjet recording maintenance liquid of the present invention may further contain a surfactant other than the compound represented by the general formula (I) described above as a surface tension adjusting agent.
Examples of the surfactant include fatty acid salts, alkyl carboxylates, alkyl sulfate esters, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene. Anionic surfactants such as sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Nonionic surface actives such as esters, acetylenic diol derivatives, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethyleneoxypropylene block copolymers Agents are preferred. When such a surfactant is included, the content in the maintenance liquid is preferably 0.5 to 10% by mass with respect to the total amount of the maintenance liquid in terms of detergency.
　本発明におけるメンテナンス液のｐＨは、７．０～９．５が好ましく、より好ましくは７．５～９．０、特に好ましくは８．０～８．８である。 The pH of the maintenance liquid in the present invention is preferably 7.0 to 9.5, more preferably 7.5 to 9.0, and particularly preferably 8.0 to 8.8.
　メンテナンス液のｐＨが低すぎると、本発明におけるインク組成物と混合した際に凝集を起こし易くなり、ｐＨが高すぎると、ヘッドの撥液膜を劣化させ易くなる傾向がある。 When the pH of the maintenance liquid is too low, aggregation tends to occur when mixed with the ink composition of the present invention, and when the pH is too high, the liquid repellent film of the head tends to be deteriorated.
　メンテナンス液の２５℃での粘度は、作業性の観点から、１ｍＰａ・ｓ以上５０ｍＰａ・ｓ以下であることが好ましく、より好ましくは１ｍＰａ・ｓ以上１０ｍＰａ・ｓ未満、更に好ましくは２ｍＰａ・ｓ以上５ｍＰａ・ｓ未満である。
　粘度は、ＶＩＳＣＯＭＥＴＥＲ　ＴＶ－２２（ＴＯＫＩ　ＳＡＮＧＹＯ　ＣＯ．ＬＴＤ製）を用いて２５℃で測定される値である。 The viscosity at 25 ° C. of the maintenance liquid is preferably 1 mPa · s or more and 50 mPa · s or less, more preferably 1 mPa · s or more and less than 10 mPa · s, and further preferably 2 mPa · s or more and 5 mPa · s from the viewpoint of workability. -Less than s.
The viscosity is a value measured at 25 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
　本発明のメンテナンス液は、顔料を含まない無色の液体であることが好ましい。
　また、メンテナンス液における固形分含量（２５℃）としては、特に制限はないが、洗浄後の固形物残留を防ぐ観点から、５質量％以下が好ましく、２質量％以下がより好ましい。 The maintenance liquid of the present invention is preferably a colorless liquid containing no pigment.
Moreover, there is no restriction | limiting in particular as solid content (25 degreeC) in a maintenance liquid, From a viewpoint of preventing the solid substance residue after washing | cleaning, 5 mass% or less is preferable, and 2 mass% or less is more preferable.
＜インクジェット記録用インクセット＞
　本発明のインクジェット記録用インクセットは、顔料とポリマー粒子と水とを含有するインク組成物と、既述の本発明のインクジェット記録用メンテナンス液とを設けて構成されている。本発明のインクジェット記録用インクセットは、更に、インク組成物中の成分を凝集させる凝集成分を含有する処理液を設けて好適に構成することができる。 <Ink set for inkjet recording>
The ink set for ink-jet recording of the present invention is constituted by providing an ink composition containing a pigment, polymer particles, and water, and the above-described maintenance liquid for ink-jet recording of the present invention. The ink set for inkjet recording of the present invention can be suitably configured by further providing a treatment liquid containing an aggregating component for aggregating the components in the ink composition.
　本発明のインクジェット記録用インクセットは、既述のインクジェット記録用メンテナンス液を備えた構成であることで、顔料及びポリマー粒子を含むためにインク吐出ヘッドの表面に付着しやすく、乾燥後には溶解、除去し難いインク、特に乾燥により固形化したインク固形物の溶解性に優れるので、長期に亘り安定した画像形成性が保持される。すなわち、例えばミスト状の微粒のインクが付着、乾燥固化することで、粒状インクがヘッド表面に存在する場合であっても、洗浄後ふき取る等の過程で吐出孔を閉塞したり、吐出孔付近に堆積する等の現象が防止される。 The ink set for ink-jet recording of the present invention has a structure including the above-described maintenance liquid for ink-jet recording, so that it easily adheres to the surface of the ink discharge head because it contains pigments and polymer particles, and dissolves after drying. Since the ink that is difficult to remove, particularly the solid ink solidified by drying, is excellent in solubility, a stable image forming property is maintained for a long time. That is, for example, when mist-like ink is adhered and dried and solidified, even when granular ink is present on the head surface, the discharge hole is blocked in the process of wiping after cleaning, etc. Phenomena such as accumulation are prevented.
－インク組成物－
　本発明におけるインク組成物は、顔料とポリマー粒子と水とを含有し、必要に応じて、更に、尿素やその誘導体、ワックス、又は界面活性剤等の添加剤等を用いて構成することができる。 -Ink composition-
The ink composition according to the present invention contains a pigment, polymer particles, and water, and can be constituted by using additives such as urea, a derivative thereof, a wax, or a surfactant, if necessary. .
（顔料）
　本発明における顔料としては、その種類に特に制限はなく、従来公知の有機及び無機顔料を用いることができる。例えば、アゾレーキ、アゾ顔料、フタロシアニン顔料、ペリレン及びペリノン顔料、アントラキノン顔料、キナクリドン顔料、ジオキサジン顔料、ジケトピロロピロール顔料、チオインジゴ顔料、イソインドリノン顔料、キノフタロン顔料等の多環式顔料や、塩基性染料型レーキ、酸性染料型レーキ等の染料レーキや、ニトロ顔料、ニトロソ顔料、アニリンブラック、昼光蛍光顔料等の有機顔料、並びに、酸化チタン、酸化鉄系、カーボンブラック系等の無機顔料が挙げられる。また、カラーインデックスに記載されていない顔料であっても水相に分散可能であれば、いずれも使用できる。更に、上記顔料を界面活性剤や高分子分散剤等で表面処理したものや、グラフトカーボン等も勿論使用可能である。上記顔料のうち、特に、アゾ顔料、フタロシアニン顔料、アントラキノン顔料、キナクリドン顔料、カーボンブラック系顔料を用いることが好ましい。具体的には特開２００７－１０００７１号公報記載の顔料等が挙げられる。 (Pigment)
There is no restriction | limiting in particular as a pigment in this invention, A conventionally well-known organic and inorganic pigment can be used. For example, polycyclic pigments such as azo lakes, azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, basic Examples include dye lakes such as dye type lakes and acid dye type lakes, organic pigments such as nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments, and inorganic pigments such as titanium oxide, iron oxide, and carbon black. It is done. Any pigment not described in the color index can be used as long as it can be dispersed in the aqueous phase. Further, it is of course possible to use a pigment obtained by surface-treating the above pigment with a surfactant, a polymer dispersing agent or the like, or graft carbon. Among the above pigments, it is particularly preferable to use an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, or a carbon black pigment. Specific examples include pigments described in JP-A No. 2007-1000007.
（分散剤）
　インク組成物においては、色材として含有される顔料の少なくとも一部が分散剤によって被覆された色材粒子として水系溶剤に分散されていることが好ましい。具体的には、顔料の一部又は全部を、水不溶性ポリマーで被覆して液中に分散させることが好ましい。この場合、顔料は必ずしも粒子表面の全体が被覆されている必要はなく、場合により粒子表面の少なくとも一部が被覆された状態であってもよい。 (Dispersant)
In the ink composition, it is preferable that at least a part of a pigment contained as a color material is dispersed in an aqueous solvent as color material particles coated with a dispersant. Specifically, it is preferable that a part or all of the pigment is coated with a water-insoluble polymer and dispersed in the liquid. In this case, the pigment does not necessarily need to be entirely coated on the particle surface, and may be in a state where at least a part of the particle surface is coated.
　分散剤としては、ポリマー分散剤でも低分子の界面活性剤型分散剤でもよい。ポリマー分散剤としては、水不溶性ポリマーの分散剤が好ましい。この水不溶性ポリマーは、顔料の分散が可能であれば特に制限はなく、従来公知の水不溶性ポリマーを用いることができる。水不溶性ポリマーとしては、例えば、疎水性の構成単位と親水性の構成単位との両方を含んで構成することができる。
　なお、「水不溶性」とは、２５℃の水系媒体にポリマーを混合したときに、水系媒体に溶解するポリマーの量が、混合した全ポリマーに対する質量比で１０質量％以下であることをいう。 The dispersant may be a polymer dispersant or a low molecular surfactant type dispersant. As the polymer dispersant, a water-insoluble polymer dispersant is preferable. The water-insoluble polymer is not particularly limited as long as the pigment can be dispersed, and a conventionally known water-insoluble polymer can be used. As a water-insoluble polymer, it can be comprised including both a hydrophobic structural unit and a hydrophilic structural unit, for example.
Note that “water-insoluble” means that when a polymer is mixed in an aqueous medium at 25 ° C., the amount of the polymer dissolved in the aqueous medium is 10% by mass or less based on the total mass of the mixed polymers.
　上記水不溶性ポリマーは、下記一般式（１）で表される繰り返し単位（ａ）とイオン性基を有する繰り返し単位（ｂ）とを含むポリマーであってもよい。このポリマーは、必要に応じて、更に、繰り返し単位（ａ）以外の他の疎水性繰り返し単位や非イオン性の官能基を持つ親水性繰り返し単位等の他の構造単位を含むことができる。 The water-insoluble polymer may be a polymer containing a repeating unit (a) represented by the following general formula (1) and a repeating unit (b) having an ionic group. The polymer may further contain other structural units such as a hydrophobic repeating unit other than the repeating unit (a) and a hydrophilic repeating unit having a nonionic functional group, if necessary.
　＜一般式（１）で表される繰り返し単位（ａ）＞
Figure JPOXMLDOC01-appb-C000010
  <Repeating unit (a) represented by general formula (1)>
Figure JPOXMLDOC01-appb-C000010
　一般式（１）において、Ｒ１は水素原子、メチル基、又はハロゲン原子（例えば、塩素原子、臭素原子、ヨウ素原子等）を表し、Ｌ１は、＊－ＣＯＯ－、＊－ＯＣＯ－、＊－ＣＯＮＲ２－、＊－Ｏ－、又は置換もしくは無置換のフェニレン基を表し、Ｒ２は水素原子、又は炭素数１～１０のアルキル基を表す。なお、Ｌ１で表される基中の＊印は、主鎖に連結する結合手を表す。Ｌ２は、単結合、又は２価の連結基を表す。Ａｒは、芳香環から誘導される１価の基を表す。 In the general formula (1), R 1 represents a hydrogen atom, a methyl group, or a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), and L 1 represents * —COO—, * —OCO—, * —CONR 2 —, * —O—, or a substituted or unsubstituted phenylene group, and R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Incidentally, symbol * in the group represented by L 1 represents a connecting point with the main chain. L 2 represents a single bond or a divalent linking group. Ar represents a monovalent group derived from an aromatic ring.
　上記一般式（１）において、Ｒ１は水素原子、メチル基、又はハロゲン原子を表し、好ましくはメチル基を表す。 In the general formula (1), R 1 represents a hydrogen atom, a methyl group, or a halogen atom, preferably a methyl group.
　Ｌ１は、＊－ＣＯＯ－、＊－ＯＣＯ－、＊－ＣＯＮＲ２－、＊－Ｏ－、又は置換もしくは無置換のフェニレン基を表す。Ｌ１がフェニレン基を表す場合、無置換が好ましい。Ｒ２は水素原子、又は炭素数１～１０のアルキル基を表す。 L 1 represents * —COO—, * —OCO—, * —CONR 2 —, * —O—, or a substituted or unsubstituted phenylene group. When L 1 represents a phenylene group, unsubstituted is preferred. R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
　Ｌ２は、単結合、又は２価の連結基を表す。上記２価の連結基としては、好ましくは炭素数１～３０の連結基であり、より好ましくは炭素数１～２５の連結基であり、更に好ましくは炭素数１～２０の連結基であり、特に好ましくは炭素数１～１５の連結基である。
　中でも、最も好ましくは、炭素数１～２５（より好ましくは１～１０）のアルキレンオキシ基、イミノ基（－ＮＨ－）、スルファモイル基、及び、炭素数１～２０（より好ましくは１～１５）のアルキレン基やエチレンオキシド基［－(ＣＨ２ＣＨ２Ｏ)ｎ－，ｎ＝１～６］等の、アルキレン基を含む２価の連結基等、並びにこれらの２種以上を組み合わせた基等である。 L 2 represents a single bond or a divalent linking group. The divalent linking group is preferably a linking group having 1 to 30 carbon atoms, more preferably a linking group having 1 to 25 carbon atoms, still more preferably a linking group having 1 to 20 carbon atoms, Particularly preferred is a linking group having 1 to 15 carbon atoms.
Among them, most preferably, an alkyleneoxy group having 1 to 25 carbon atoms (more preferably 1 to 10), an imino group (—NH—), a sulfamoyl group, and 1 to 20 carbon atoms (more preferably 1 to 15). A divalent linking group containing an alkylene group, such as an alkylene group or an ethylene oxide group [— (CH 2 CH 2 O) n —, n = 1 to 6], etc., and a group combining two or more of these is there.
　Ａｒは、芳香環から誘導される１価の基を表す。Ａｒで表される１価の基の芳香環としては、特に限定されないが、ベンゼン環、炭素数８以上の縮環型芳香環、又はヘテロ環が縮環した芳香環が挙げられる。 Ar represents a monovalent group derived from an aromatic ring. The aromatic ring of the monovalent group represented by Ar is not particularly limited, and examples thereof include a benzene ring, a condensed aromatic ring having 8 or more carbon atoms, or an aromatic ring condensed with a hetero ring.
　上記「炭素数８以上の縮環型芳香環」は、少なくとも２以上のベンゼン環が縮環した芳香環、少なくとも１種の芳香環と該芳香環に縮環して脂環式炭化水素で環が構成された炭素数８以上の芳香族化合物である。具体的な例としては、ナフタレン、アントラセン、フルオレン、フェナントレン、アセナフテン等が挙げられる。 The “condensed aromatic ring having 8 or more carbon atoms” includes an aromatic ring in which at least two benzene rings are condensed, at least one aromatic ring and a condensed alicyclic hydrocarbon ring. Is an aromatic compound having 8 or more carbon atoms. Specific examples include naphthalene, anthracene, fluorene, phenanthrene, acenaphthene and the like.
　上記「ヘテロ環が縮環した芳香環」とは、ヘテロ原子を含まない芳香族化合物（好ましくはベンゼン環）と、ヘテロ原子を有する環状化合物とが縮環した化合物である。ここで、ヘテロ原子を有する環状化合物は、５員環又は６員環であることが好ましい。ヘテロ原子としては、窒素原子、酸素原子、又は硫黄原子が好ましい。ヘテロ原子を有する環状化合物は、複数のヘテロ原子を有していてもよい。この場合、ヘテロ原子は互いに同じでも異なっていてもよい。
　芳香環が縮環したヘテロ環の具体例としては、フタルイミド、アクリドン、カルバゾール、ベンゾオキサゾール、ベンゾチアゾール等が挙げられる。 The “aromatic ring condensed with a heterocycle” is a compound in which an aromatic compound not containing a hetero atom (preferably a benzene ring) and a cyclic compound having a hetero atom are condensed. Here, the cyclic compound having a hetero atom is preferably a 5-membered ring or a 6-membered ring. As a hetero atom, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable. The cyclic compound having a hetero atom may have a plurality of hetero atoms. In this case, the heteroatoms may be the same or different from each other.
Specific examples of the heterocyclic ring condensed with an aromatic ring include phthalimide, acridone, carbazole, benzoxazole, and benzothiazole.
　上記一般式（１）で表される繰り返し単位（ａ）を形成するモノマーの具体例としては、（メタ）アクリレート類、（メタ）アクリルアミド類、スチレン類、及びビニルエステル類等のビニルモノマー類を挙げることができる。 Specific examples of the monomer that forms the repeating unit (a) represented by the general formula (1) include vinyl monomers such as (meth) acrylates, (meth) acrylamides, styrenes, and vinyl esters. Can be mentioned.
　本発明において、一般式（１）で表される繰り返し単位（ａ）では、芳香環は連結基を介して水不溶性ポリマーの主鎖の一部をなす原子と結合され、水不溶性ポリマーの主鎖の一部をなす原子に直接結合しない構造を有するので、疎水性の芳香環と親水性構造単位との間に適切な距離が維持されるため、水不溶性ポリマーと顔料との間で相互作用が生じやすく、強固に吸着して分散性が更に向上する。 In the present invention, in the repeating unit (a) represented by the general formula (1), the aromatic ring is bonded to an atom forming a part of the main chain of the water-insoluble polymer through a linking group, and the main chain of the water-insoluble polymer Since it has a structure that is not directly bonded to the atoms that form part of the structure, an appropriate distance is maintained between the hydrophobic aromatic ring and the hydrophilic structural unit, so that there is an interaction between the water-insoluble polymer and the pigment. It tends to occur and is strongly adsorbed to further improve dispersibility.
　更には、上記一般式（１）で表される繰り返し単位（ａ）を形成するモノマーの具体例としては、下記のモノマー等を挙げることができる。但し、本発明においては、これらに限定されるものではない。 Furthermore, specific examples of the monomer that forms the repeating unit (a) represented by the general formula (1) include the following monomers. However, the present invention is not limited to these.
Figure JPOXMLDOC01-appb-C000011
 
Figure JPOXMLDOC01-appb-C000012
 
Figure JPOXMLDOC01-appb-C000011
 
Figure JPOXMLDOC01-appb-C000012
 
　上記一般式（１）で表される繰り返し単位（ａ）としては、被覆された顔料の分散安定性の観点から、ベンジル（メタ）アクリレート、フェノキシエチルアクリレート、フェノキシエチルメタクリレート、または、一般式（１）においてＡｒがアクリドン又はフタルイミドから誘導される１価の基であるものが好ましい。 As the repeating unit (a) represented by the general formula (1), from the viewpoint of dispersion stability of the coated pigment, benzyl (meth) acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, or the general formula (1) In which Ar is a monovalent group derived from acridone or phthalimide.
　上記繰り返し単位は、１種単独で又は２種以上を混合して用いることができる。
　上記一般式（１）で表される繰り返し単位（ａ）のポリマー中における含有割合は、ポリマーの全質量に対して、５～２５質量％の範囲が好ましく、より好ましくは１０～１８質量％の範囲である。この含有割合は、５質量％以上であると、白抜け等の画像故障の発生を顕著に抑制できる傾向となり、また、２５質量％以下とするとポリマーの重合反応溶液（例えば、メチルエチルケトン）中での溶解性低下による製造適性上の問題が生じない傾向となり好ましい。 The said repeating unit can be used individually by 1 type or in mixture of 2 or more types.
The content of the repeating unit (a) represented by the general formula (1) in the polymer is preferably in the range of 5 to 25% by mass, more preferably 10 to 18% by mass with respect to the total mass of the polymer. It is a range. When the content is 5% by mass or more, the occurrence of image failure such as white spots tends to be remarkably suppressed, and when the content is 25% by mass or less, the polymerization in a polymerization reaction solution (for example, methyl ethyl ketone). This is preferable because there is a tendency that problems in production suitability due to a decrease in solubility do not occur.
＜他の疎水性繰り返し単位＞
　水不溶性ポリマーは、疎水性構造単位として、上記一般式（１）で表される繰り返し単位以外の他の疎水性繰り返し単位を更に有してもよい。他の疎水性繰り返し単位としては、例えば、親水性構造単位に属しない（例えば、親水性の官能基を有しない）例えば（メタ）アクリレート類、（メタ）アクリルアミド類、スチレン類、及びビニルエステル類等のビニルモノマー類、主鎖をなす原子に連結基を介して芳香環を有する疎水性構造単位等に由来の構造単位を挙げることができる。これらの構造単位は、１種単独で又は２種以上を混合して用いることができる。 <Other hydrophobic repeating units>
The water-insoluble polymer may further have a hydrophobic repeating unit other than the repeating unit represented by the general formula (1) as a hydrophobic structural unit. Examples of other hydrophobic repeating units include, for example, those that do not belong to a hydrophilic structural unit (for example, have no hydrophilic functional group), such as (meth) acrylates, (meth) acrylamides, styrenes, and vinyl esters. And other structural units derived from vinyl monomers such as hydrophobic structural units having an aromatic ring via a linking group at the atom forming the main chain. These structural units can be used individually by 1 type or in mixture of 2 or more types.
　上記（メタ）アクリレート類としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレートが挙げられ、これらのうち（メタ）アクリル酸の炭素数１～４のアルキルエステルが好ましい。中でも、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレートが好ましく、特にメチル（メタ）アクリレート、エチル（メタ）アクリレートが好ましい。
　また、（メタ）アクリルアミド類、スチレン類、及びビニルエステル類については、特開２００１－１６２６９２号公報の段落番号［００６３］～［００６５］に記載の化合物が挙げられる。 Examples of the (meth) acrylates include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and hexyl (meth) acrylate. Of these, alkyl esters of (meth) acrylic acid having 1 to 4 carbon atoms are preferred. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are preferable, and methyl (meth) acrylate and ethyl (meth) acrylate are particularly preferable.
Examples of (meth) acrylamides, styrenes, and vinyl esters include the compounds described in paragraph numbers [0063] to [0065] of JP-A No. 2001-162692.
＜イオン性基を有する繰り返し単位（ｂ）＞
　イオン性基を有する繰り返し単位（ｂ）としては、カルボキシル基、スルホ基、ホスホネート基等のイオン性基を有するモノマーに由来する繰り返し単位が挙げられる。例えば、（メタ）アクリル酸、（メタ）アクリレート類、（メタ）アクリルアミド類、及びビニルエステル類等の、イオン性官能基を有するビニルモノマー類を挙げることができる。イオン性基を有する繰り返し単位は、対応するモノマーの重合により導入できるが、重合後のポリマー鎖にイオン性基を導入したものでもよい。これらのうち、アクリル酸、メタクリル酸に由来の繰り返し単位が好ましく、アクリル酸由来の構造単位もしくはメタクリル酸由来の構造単位のいずれか又は両方を含むことが好ましい。 <Repeating unit (b) having ionic group>
Examples of the repeating unit (b) having an ionic group include a repeating unit derived from a monomer having an ionic group such as a carboxyl group, a sulfo group, or a phosphonate group. Examples thereof include vinyl monomers having an ionic functional group such as (meth) acrylic acid, (meth) acrylates, (meth) acrylamides, and vinyl esters. The repeating unit having an ionic group can be introduced by polymerization of the corresponding monomer, but may be one in which an ionic group is introduced into the polymer chain after polymerization. Among these, the repeating unit derived from acrylic acid and methacrylic acid is preferable, and it is preferable to include one or both of a structural unit derived from acrylic acid and a structural unit derived from methacrylic acid.
　このポリマーは、イオン性基を有する繰り返し単位（ｂ）の割合がポリマー全質量の１５質量％以下であって、イオン性基を有する繰り返し単位として少なくとも（メタ）アクリル酸由来の構造単位を含む態様が好ましい。イオン性基を有する繰り返し単位（ｂ）の含有量がポリマー全質量の１５質量％以下であると、分散安定性に優れる。中でも、イオン性基を有する繰り返し単位（ｂ）の割合は、分散安定性の観点から、５質量％以上１５質量％以下が好ましく、７質量％以上１３質量％以下がより好ましい。 In this polymer, the proportion of the repeating unit (b) having an ionic group is 15% by mass or less of the total mass of the polymer, and the polymer contains at least a structural unit derived from (meth) acrylic acid as the repeating unit having an ionic group. Is preferred. When the content of the repeating unit (b) having an ionic group is 15% by mass or less of the total mass of the polymer, the dispersion stability is excellent. Especially, the ratio of the repeating unit (b) having an ionic group is preferably 5% by mass or more and 15% by mass or less, and more preferably 7% by mass or more and 13% by mass or less from the viewpoint of dispersion stability.
　このポリマーは、水性のインク組成物中において安定的に存在することができ、例えばインクジェットヘッド等での凝集物の付着、堆積を緩和し、付着した凝集物の除去性にも優れる。このような観点から、上記一般式（１）で表される繰り返し単位（ａ）以外の疎水性構造単位、及び上記「イオン性基を有する繰り返し単位（ｂ）」以外の他の親水性構造単位を更に有していてもよい。 This polymer can be stably present in an aqueous ink composition, and for example, the adhesion and deposition of aggregates in an ink jet head or the like is eased, and the removability of the adhered aggregates is excellent. From such a viewpoint, the hydrophobic structural unit other than the repeating unit (a) represented by the general formula (1) and the hydrophilic structural unit other than the above “repeating unit (b) having an ionic group” May further be included.
＜親水性繰り返し単位＞
　上記他の親水性構成単位としては、非イオン性の親水性基を有するモノマーに由来の繰り返し単位が挙げられ、例えば、親水性の官能基を有する（メタ）アクリレート類、（メタ）アクリルアミド類、及びビニルエステル類等の、親水性の官能基を有するビニルモノマー類を挙げることができる。
　「親水性の官能基」としては、水酸基、アミノ基、（窒素原子が無置換の）アミド基、及び後述のポリエチレンオキシド、ポリプロピレンオキシド等のアルキレンオキシドが挙げられる。 <Hydrophilic repeating unit>
Examples of the other hydrophilic structural unit include a repeating unit derived from a monomer having a nonionic hydrophilic group. For example, (meth) acrylates having a hydrophilic functional group, (meth) acrylamides, And vinyl monomers having a hydrophilic functional group, such as vinyl esters.
Examples of the “hydrophilic functional group” include a hydroxyl group, an amino group, an amide group (unsubstituted with a nitrogen atom), and alkylene oxides such as polyethylene oxide and polypropylene oxide described later.
　非イオン性の親水性基を有する親水性繰り返し単位を形成するモノマーは、エチレン性不飽和結合等の重合体を形成しうる官能基と非イオン性の親水性の官能基とを有していれば、特に制限はなく、公知のモノマーから選択することができる。具体的な例としては、ヒドロキシエチル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、（メタ）アクリルアミド、アミノエチルアクリレート、アミノプロピルアクリレート、アルキレンオキシド重合体を含有する（メタ）アクリレートを好適に挙げることができる。
　非イオン性の親水性基を有する親水性繰り返し単位は、対応するモノマーの重合により形成することができるが、重合後のポリマー鎖に親水性の官能基を導入してもよい。 The monomer forming the hydrophilic repeating unit having a nonionic hydrophilic group may have a functional group capable of forming a polymer such as an ethylenically unsaturated bond and a nonionic hydrophilic functional group. For example, there is no particular limitation, and it can be selected from known monomers. Specific examples include hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylamide, aminoethyl acrylate, aminopropyl acrylate, and (meth) acrylate containing an alkylene oxide polymer. Can do.
The hydrophilic repeating unit having a nonionic hydrophilic group can be formed by polymerization of the corresponding monomer, but a hydrophilic functional group may be introduced into the polymer chain after polymerization.
　非イオン性の親水性基を有する親水性繰り返し単位は、アルキレンオキシド構造を有する親水性の構造単位がより好ましい。アルキレンオキシド構造のアルキレン部位としては、親水性の観点から、炭素数１～６のアルキレンが好ましく、炭素数２～６のアルキレンがより好ましく、炭素数２～４のアルキレンが特に好ましい。また、アルキレンオキシド構造の重合度としては、１～１２０が好ましく、１～６０がより好ましく、１～３０が特に好ましい。
　また、非イオン性の親水性基を有する親水性繰り返し単位は、水酸基を含む親水性の繰り返し単位であることも好ましい態様である。繰り返し単位中の水酸基数としては、特に制限はなく、水不溶性ポリマーの親水性、重合時の溶剤や他のモノマーとの相溶性の観点から、１～４が好ましく、１～３がより好ましく、１～２が特に好ましい。 The hydrophilic repeating unit having a nonionic hydrophilic group is more preferably a hydrophilic structural unit having an alkylene oxide structure. The alkylene moiety of the alkylene oxide structure is preferably an alkylene having 1 to 6 carbon atoms, more preferably an alkylene having 2 to 6 carbon atoms, and particularly preferably an alkylene having 2 to 4 carbon atoms from the viewpoint of hydrophilicity. The degree of polymerization of the alkylene oxide structure is preferably 1 to 120, more preferably 1 to 60, and particularly preferably 1 to 30.
Moreover, it is also a preferable aspect that the hydrophilic repeating unit having a nonionic hydrophilic group is a hydrophilic repeating unit containing a hydroxyl group. The number of hydroxyl groups in the repeating unit is not particularly limited, and is preferably 1 to 4, more preferably 1 to 3, from the viewpoint of hydrophilicity of the water-insoluble polymer and compatibility with the solvent and other monomers during polymerization. 1-2 is particularly preferred.
　水不溶性ポリマーにおいて、親水性繰り返し単位と疎水性繰り返し単位（上記一般式（１）で表される構造繰り返しを含む）との組成は、各々の親水性、疎水性の程度にも影響するが、親水性繰り返し単位の割合が水不溶性ポリマーの質量に対して１５質量％以下であることが好ましい。このとき、疎水性繰り返し単位は、水不溶性ポリマーの質量全体に対して、８０質量％を超える割合であるのが好ましく、８５質量％以上であるのがより好ましい。親水性繰り返し単位の含有量が１５質量％以下であると、単独で水性媒体中に溶解する成分量が抑えられ、顔料の分散等の諸性能が良好になり、インクジェット記録時には良好なインク吐出性が得られる。親水性繰り返し単位の好ましい含有割合は、水不溶性ポリマーの全質量に対して、０質量％を超え１５質量％以下であり、より好ましくは５～１５質量％であり、特に好ましくは８～１２質量％である。 In the water-insoluble polymer, the composition of the hydrophilic repeating unit and the hydrophobic repeating unit (including the structural repeat represented by the general formula (1)) affects the degree of hydrophilicity and hydrophobicity of each, The ratio of the hydrophilic repeating unit is preferably 15% by mass or less with respect to the mass of the water-insoluble polymer. At this time, it is preferable that a hydrophobic repeating unit is a ratio exceeding 80 mass% with respect to the whole mass of a water-insoluble polymer, and it is more preferable that it is 85 mass% or more. When the content of the hydrophilic repeating unit is 15% by mass or less, the amount of the component dissolved alone in the aqueous medium is suppressed, and various properties such as pigment dispersion are improved. Is obtained. A preferable content ratio of the hydrophilic repeating unit is more than 0% by mass and 15% by mass or less, more preferably 5 to 15% by mass, and particularly preferably 8 to 12% by mass with respect to the total mass of the water-insoluble polymer. %.
　芳香環の水不溶性ポリマー中に含まれる含有割合は、水不溶性ポリマーの全質量に対して、２７質量％以下であるのが好ましく、２５質量％以下であるのがより好ましく、２０質量％以下であることが更に好ましい。中でも、１５～２０質量％であるのが好ましく、１７～２０質量％の範囲がより好ましい。芳香族環の含有割合が上記範囲内であると、耐擦過性が向上する。 The content of the aromatic ring contained in the water-insoluble polymer is preferably 27% by mass or less, more preferably 25% by mass or less, and more preferably 20% by mass or less, based on the total mass of the water-insoluble polymer. More preferably it is. In particular, the content is preferably 15 to 20% by mass, and more preferably in the range of 17 to 20% by mass. When the content of the aromatic ring is within the above range, the scratch resistance is improved.
　以下、ポリマーの具体例を列挙する。但し、下記に限定されるものではない。
・フェノキシエチルアクリレート／メチルメタクリレート／アクリル酸共重合体（５０／４５／５［質量比］）
・フェノキシエチルアクリレート／ベンジルメタクリレート／イソブチルメタクリレート／メタクリル酸共重合体（３０／３５／２９／６［質量比］）
・フェノキシエチルメタクリレート／イソブチルメタクリレート／メタクリル酸共重合体（５０／４４／６［質量比］）
・フェノキシエチルアクリレート／メチルメタクリレート／エチルアクリレート／アクリル酸共重合体（３０／５５／１０／５［質量比］）
・ベンジルメタクリレート／メチルメタクリレート／メタクリル酸共重合体（６０／３０／１０［質量比］） Specific examples of the polymer are listed below. However, it is not limited to the following.
・ Phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (50/45/5 [mass ratio])
・ Phenoxyethyl acrylate / benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (30/35/29/6 [mass ratio])
・ Phenoxyethyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (50/44/6 [mass ratio])
・ Phenoxyethyl acrylate / methyl methacrylate / ethyl acrylate / acrylic acid copolymer (30/55/10/5 [mass ratio])
・ Benzyl methacrylate / methyl methacrylate / methacrylic acid copolymer (60/30/10 [mass ratio])
　本発明における水不溶性ポリマーの酸価としては、顔料分散性、保存安定性の観点から、３０ｍｇＫＯＨ／ｇ以上１００ｍｇＫＯＨ／ｇ以下であることが好ましく、３０ｍｇＫＯＨ／ｇ以上８５ｍｇＫＯＨ／ｇ以下であることがより好ましく、５０ｍｇＫＯＨ／ｇ以上８５ｍｇＫＯＨ／ｇ以下であることが特に好ましい。
　酸価とは、水不溶性ポリマーの１ｇを完全に中和するのに要するＫＯＨの質量（ｍｇ）で定義され、ＪＩＳ規格（ＪＩＳ　Ｋ　００７０、１９９２）記載の方法により測定されるものである。 The acid value of the water-insoluble polymer in the present invention is preferably from 30 mgKOH / g to 100 mgKOH / g, more preferably from 30 mgKOH / g to 85 mgKOH / g from the viewpoint of pigment dispersibility and storage stability. It is preferably 50 mgKOH / g or more and 85 mgKOH / g or less.
The acid value is defined by the mass (mg) of KOH required to completely neutralize 1 g of the water-insoluble polymer, and is measured by the method described in JIS standard (JIS K 0070, 1992).
　本発明における水不溶性ポリマーの分子量としては、重量平均分子量（Ｍｗ）で３万以上が好ましく、３万～１５万がより好ましく、更に好ましくは３万～１０万であり、特に好ましくは３万～８万である。 The molecular weight of the water-insoluble polymer in the present invention is preferably 30,000 or more in terms of weight average molecular weight (Mw), more preferably 30,000 to 150,000, still more preferably 30,000 to 100,000, and particularly preferably 30,000 to 100,000. 80,000.
　水不溶性ポリマーは、種々の重合方法、例えば溶液重合、沈澱重合、懸濁重合、沈殿重合、塊状重合、乳化重合により合成することができる。重合反応は、回分式、半連続式、連続式等の公知の操作で行なうことができる。重合の開始方法は、ラジカル開始剤を用いる方法、光又は放射線を照射する方法等がある。これらの重合方法、重合の開始方法は、例えば、鶴田禎二「高分子合成方法」改定版（日刊工業新聞社刊、１９７１）や大津隆行、木下雅悦共著「高分子合成の実験法」化学同人、昭和４７年刊、１２４～１５４頁に記載されている。 The water-insoluble polymer can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system. The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are described in, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu and Masato Kinoshita, “Experimental Methods for Polymer Synthesis” , Published in 1972, pages 124-154.
　顔料のインク組成物中における含有量としては、インク組成物の全質量に対して、０．１～１５質量％の範囲が好ましく、１～１０質量％の範囲がより好ましい。 The content of the pigment in the ink composition is preferably in the range of 0.1 to 15% by mass and more preferably in the range of 1 to 10% by mass with respect to the total mass of the ink composition.
（ポリマー粒子）
　本発明におけるインク組成物は、ポリマー粒子の少なくとも一種を含有する。水に対して非水溶性又は難水溶性のポリマー粒子を、顔料を被う上記樹脂とは別に含有することによって、インク組成物の記録媒体への定着性、及び形成画像の耐擦過性がより向上する。その一方、インクの吐出ヘッドへの付着、堆積が起きやすくなるが、本発明のインクセットは既述のメンテナンス液を用いて構成されるので、長期に亘りインクの吐出曲がりや不吐出等の吐出不良の発生を抑え、良好な画像形成性を保持することができる。 (Polymer particles)
The ink composition in the present invention contains at least one kind of polymer particles. By containing the water-insoluble or poorly water-soluble polymer particles separately from the resin that covers the pigment, the fixability of the ink composition to the recording medium and the scratch resistance of the formed image are further improved. improves. On the other hand, the ink is likely to adhere to and accumulate on the ejection head. However, since the ink set of the present invention is configured using the above-described maintenance liquid, ejection such as ink ejection bending or non-ejection over a long period of time. The occurrence of defects can be suppressed and good image forming properties can be maintained.
　ポリマーが「非水溶性又は難水溶性」であるとは、樹脂を１０５℃で２時間乾燥させた後、２５℃の水１００ｇ中に溶解させたときに、その溶解量が１５ｇ以下であることをいう。インクの連続吐出性及び吐出安定性が向上する観点から、上記溶解量は好ましくは１０ｇ以下であり、更に好ましくは５ｇ以下であり、特に好ましくは１ｇ以下である。上記溶解量は、水不溶性ポリマーの塩生成基の種類に応じて、水酸化ナトリウム又は酢酸で１００％中和した時の溶解量である。 The polymer is “water-insoluble or sparingly water-soluble” when the resin is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C., the amount of dissolution is 15 g or less. Say. From the viewpoint of improving the continuous ejection property and ejection stability of the ink, the dissolution amount is preferably 10 g or less, more preferably 5 g or less, and particularly preferably 1 g or less. The dissolution amount is the dissolution amount when neutralized with sodium hydroxide or acetic acid according to the kind of the salt-forming group of the water-insoluble polymer.
　水不溶性のポリマー粒子としては、例えば、熱可塑性、熱硬化性あるいは変性のアクリル系、エポキシ系、ポリウレタン系、ポリエーテル系、ポリアミド系、不飽和ポリエステル系、フェノール系、シリコーン系、又はフッ素系の樹脂、塩化ビニル、酢酸ビニル、ポリビニルアルコール、又はポリビニルブチラール等のポリビニル系樹脂、アルキド樹脂、フタル酸樹脂等のポリエステル系樹脂、メラミン樹脂、メラミンホルムアルデヒド樹脂、アミノアルキド共縮合樹脂、ユリア樹脂、尿素樹脂等のアミノ系材料、あるいはそれらの共重合体又は混合物等の樹脂の粒子が挙げられる。これらのうち、アニオン性のアクリル系樹脂は、例えば、アニオン性基を有するアクリルモノマー（アニオン性基含有アクリルモノマー）及び必要に応じて該アニオン性基含有アクリルモノマーと共重合可能な他のモノマーを溶剤中で重合して得られる。上記アニオン性基含有アクリルモノマーとしては、例えば、カルボキシル基、スルホン酸基、及びホスホン酸基からなる群より選ばれる１以上を有するアクリルモノマーが挙げられる。中でも、カルボキシル基を有するアクリルモノマー（例えば、アクリル酸、メタクリル酸、クロトン酸、エタアクリル酸、プロピルアクリル酸、イソプロピルアクリル酸、イタコン酸、フマル酸等）が好ましく、特にはアクリル酸又はメタクリル酸が好ましい。 Examples of water-insoluble polymer particles include thermoplastic, thermosetting or modified acrylic, epoxy, polyurethane, polyether, polyamide, unsaturated polyester, phenol, silicone, or fluorine. Resins, polyvinyl resins such as vinyl chloride, vinyl acetate, polyvinyl alcohol or polyvinyl butyral, polyester resins such as alkyd resins and phthalic resins, melamine resins, melamine formaldehyde resins, aminoalkyd co-condensation resins, urea resins, urea resins Examples thereof include resin particles such as amino-based materials such as copolymers or copolymers or mixtures thereof. Among these, anionic acrylic resins include, for example, an acrylic monomer having an anionic group (anionic group-containing acrylic monomer) and, if necessary, other monomers copolymerizable with the anionic group-containing acrylic monomer. Obtained by polymerization in a solvent. Examples of the anionic group-containing acrylic monomer include acrylic monomers having one or more selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphonic acid group. Among them, an acrylic monomer having a carboxyl group (for example, acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid, etc.) is preferable, and acrylic acid or methacrylic acid is particularly preferable. preferable.
　水不溶性のポリマー粒子としては、吐出安定性及び顔料を含む系の液安定性（特に分散安定性）の観点から、自己分散性ポリマー粒子が好ましい。自己分散性ポリマー（以下、自己分散性樹脂という。）とは、界面活性剤の不存在下、転相乳化法により分散状態としたとき、ポリマー自身の官能基（特に酸性基又はその塩）により、水性媒体中で分散状態となりうる水不溶性ポリマーをいう。
　ここで分散状態とは、水性媒体中に水不溶性ポリマーが液体状態で分散された乳化状態（エマルション）、及び、水性媒体中に水不溶性ポリマーが固体状態で分散された分散状態（サスペンジョン）の両方の状態を含むものである。
　自己分散性樹脂においては、インク組成物に含有されたときのインク定着性の観点から、水不溶性ポリマーが固体状態で分散された分散状態となりうる自己分散性樹脂であることが好ましい。 The water-insoluble polymer particles are preferably self-dispersing polymer particles from the viewpoints of ejection stability and liquid stability (particularly dispersion stability) of a system containing a pigment. A self-dispersing polymer (hereinafter referred to as a self-dispersing resin) is a functional group (especially an acidic group or a salt thereof) of the polymer itself when it is dispersed by a phase inversion emulsification method in the absence of a surfactant. A water-insoluble polymer that can be dispersed in an aqueous medium.
Here, the dispersed state means both an emulsified state (emulsion) in which a water-insoluble polymer is dispersed in an aqueous medium and a dispersed state (suspension) in which a water-insoluble polymer is dispersed in an aqueous medium. It includes the state of.
The self-dispersing resin is preferably a self-dispersing resin that can be in a dispersed state in which a water-insoluble polymer is dispersed in a solid state from the viewpoint of ink fixing properties when contained in the ink composition.
　自己分散性樹脂の乳化又は分散状態、すなわち自己分散性樹脂の水性分散物の調製方法としては、転相乳化法が挙げられる。転相乳化法としては、例えば、自己分散性樹脂を溶剤（例えば、水溶性有機溶剤等）中に溶解又は分散させた後、界面活性剤を添加せずにそのまま水中に投入し、自己分散性樹脂が有する塩生成基（例えば、酸性基）を中和した状態で、攪拌、混合し、上記溶剤を除去した後、乳化又は分散状態となった水性分散物を得る方法が挙げられる。 As a method for preparing an emulsified or dispersed state of the self-dispersing resin, that is, an aqueous dispersion of the self-dispersing resin, a phase inversion emulsification method may be mentioned. As the phase inversion emulsification method, for example, a self-dispersing resin is dissolved or dispersed in a solvent (for example, a water-soluble organic solvent) and then poured into water as it is without adding a surfactant. Examples include a method of obtaining an aqueous dispersion in an emulsified or dispersed state after stirring and mixing in a state in which a salt-forming group (for example, an acidic group) of the resin is neutralized and mixing to remove the solvent.
　また、自己分散性樹脂における安定な乳化又は分散状態とは、水不溶性ポリマー３０ｇを７０ｇの有機溶剤（例えば、メチルエチルケトン）に溶解した溶液、該水不溶性ポリマーの塩生成基を１００％中和できる中和剤（塩生成基がアニオン性であれば水酸化ナトリウム、カチオン性であれば酢酸）、及び水２００ｇを混合、攪拌（装置：攪拌羽根付き攪拌装置、回転数２００ｒｐｍ、３０分間、２５℃）した後、該混合液から該有機溶剤を除去した後でも、乳化又は分散状態が、２５℃で、少なくとも１週間安定に存在し、沈殿の発生が目視で確認できない状態であることをいう。 In addition, a stable emulsified or dispersed state in the self-dispersing resin is a solution in which 30 g of a water-insoluble polymer is dissolved in 70 g of an organic solvent (for example, methyl ethyl ketone), and the salt-forming group of the water-insoluble polymer can be neutralized 100%. Mixing agent (sodium hydroxide if the salt-forming group is anionic, acetic acid if it is cationic) and water 200g, stirring (device: stirring device with stirring blades, rotation speed 200rpm, 30 minutes, 25 ° C) Then, even after removing the organic solvent from the mixed solution, it means that the emulsified or dispersed state is stably present at 25 ° C. for at least one week, and the occurrence of precipitation cannot be visually confirmed.
　また、自己分散性樹脂における乳化又は分散状態の安定性は、遠心分離による沈降の加速試験によっても確認することができる。遠心分離による、沈降の加速試験による安定性は、例えば、上記の方法により得られたポリマー粒子の水性分散物を、固形分濃度２５質量％に調整した後、１２０００ｒｐｍで一時間遠心分離し、遠心分離後の上澄みの固形分濃度を測定することによって評価できる。
　遠心分離前の固形分濃度に対する遠心分離後の固形分濃度の比が大きければ（１に近い数値であれば）、遠心分離によるポリマー粒子の沈降が生じない、すなわち、ポリマー粒子の水性分散物がより安定であることを意味する。本発明においては、遠心分離前後での固形分濃度の比が０．８以上であることが好ましく、０．９以上であることがより好ましく、０．９５以上であることが特に好ましい。 The stability of the emulsified or dispersed state in the self-dispersing resin can also be confirmed by an accelerated sedimentation test by centrifugation. The stability of the sedimentation acceleration test by centrifugation is, for example, adjusted by adjusting the aqueous dispersion of polymer particles obtained by the above method to a solid concentration of 25% by mass, and then centrifuging at 12,000 rpm for 1 hour. It can be evaluated by measuring the solid content concentration of the supernatant after separation.
If the ratio of the solid content concentration after centrifugation to the solid content concentration before centrifugation is large (a value close to 1), the sedimentation of the polymer particles by centrifugation does not occur, that is, the aqueous dispersion of polymer particles Means more stable. In the present invention, the ratio of the solid content concentration before and after centrifugation is preferably 0.8 or more, more preferably 0.9 or more, and particularly preferably 0.95 or more.
　自己分散性樹脂は、分散状態としたときに水溶性を示す水溶性成分の含有量が１０質量％以下であることが好ましく、８質量％以下であることがより好ましく、６質量％以下であることが更に好ましい。水溶性成分を１０質量％以下とすることで、ポリマー粒子の膨潤やポリマー粒子同士の融着を効果的に抑制し、より安定な分散状態を維持することができる。また、インク組成物の粘度上昇を抑制でき、例えば、インク組成物をインクジェット法に適用する場合に、吐出安定性がより良好になる。
　ここで水溶性成分とは、自己分散性樹脂に含有される化合物であって、自己分散性樹脂を分散状態にした場合に水に溶解する化合物をいう。上記水溶性成分は自己分散性樹脂を製造する際に、副生又は混入する水溶性の化合物である。 The self-dispersing resin preferably has a water-soluble component content that is water-soluble when in a dispersed state of 10% by mass or less, more preferably 8% by mass or less, and 6% by mass or less. More preferably. By setting the water-soluble component to 10% by mass or less, swelling of polymer particles and fusion of polymer particles can be effectively suppressed, and a more stable dispersion state can be maintained. In addition, an increase in the viscosity of the ink composition can be suppressed. For example, when the ink composition is applied to an ink jet method, the ejection stability becomes better.
Here, the water-soluble component is a compound contained in the self-dispersing resin and is a compound that dissolves in water when the self-dispersing resin is in a dispersed state. The water-soluble component is a water-soluble compound that is by-produced or mixed in the production of the self-dispersing resin.
　水不溶性樹脂の主鎖骨格としては、特に制限はなく、例えば、ビニルポリマー、縮合系ポリマー（エポキシ樹脂、ポリエステル、ポリウレタン、ポリアミド、セルロース、ポリエーテル、ポリウレア、ポリイミド、ポリカーボネート等）が挙げられる。中でも、特にビニルポリマーが好ましい。 The main chain skeleton of the water-insoluble resin is not particularly limited, and examples thereof include vinyl polymers and condensation polymers (epoxy resins, polyesters, polyurethanes, polyamides, celluloses, polyethers, polyureas, polyimides, polycarbonates, etc.). Of these, vinyl polymers are particularly preferable.
　ビニルポリマー及びビニルポリマーの製造に用いられるモノマーの好適な例としては、特開２００１－１８１５４９号公報及び特開２００２－８８２９４号公報に記載されているものを挙げることができる。また、解離性基（あるいは解離性基に誘導できる置換基）を有する連鎖移動剤や重合開始剤、イニファーターを用いたビニルモノマーのラジカル重合や、開始剤あるいは停止剤のどちらかに解離性基（あるいは解離性基に誘導できる置換基）を有する化合物を用いたイオン重合によって高分子鎖の末端に解離性基を導入したビニルポリマーも使用できる。
　また、縮合系ポリマーと縮合系ポリマーの製造に用いられるモノマーの好適な例としては、特開２００１－２４７７８７号公報に記載されているものを挙げることができる。 Preferable examples of the vinyl polymer and the monomer used for producing the vinyl polymer include those described in JP-A Nos. 2001-181549 and 2002-88294. In addition, radical transfer of vinyl monomers using dissociable groups (or substituents that can be induced to dissociable groups), polymerization initiators, and iniferters, or dissociable groups on either initiators or terminators. A vinyl polymer in which a dissociable group is introduced at the end of a polymer chain by ionic polymerization using a compound having (or a substituent that can be derived from a dissociable group) can also be used.
Further, preferred examples of the condensation polymer and the monomer used for the production of the condensation polymer include those described in JP-A-2001-247787.
　自己分散性樹脂の粒子は、自己分散性の観点から、親水性の構成単位と芳香族基含有モノマー又は環状脂肪族基含有モノマーに由来する構成単位とを含む水不溶性ポリマーを含むことが好ましい。 The self-dispersing resin particles preferably include a water-insoluble polymer including a hydrophilic structural unit and a structural unit derived from an aromatic group-containing monomer or a cyclic aliphatic group-containing monomer from the viewpoint of self-dispersibility.
　上記「親水性の構成単位」は、親水性基含有モノマーに由来するものであれば特に制限はなく、１種の親水性基含有モノマーに由来するものであっても、２種以上の親水性基含有モノマーに由来するものであってもよい。上記親水性基としては、特に制限はなく、解離性基であってもノニオン性親水性基であってもよい。上記親水性基は、自己分散促進の観点、形成された乳化又は分散状態の安定性の観点から、解離性基であることが好ましく、アニオン性の解離基であることがより好ましい。上記解離性基としては、カルボキシル基、リン酸基、スルホン酸基等が挙げられ、中でも、インク組成物を構成した場合の定着性の観点から、カルボキシル基が好ましい。 The “hydrophilic structural unit” is not particularly limited as long as it is derived from a hydrophilic group-containing monomer, and even if it is derived from one kind of hydrophilic group-containing monomer, two or more hydrophilic groups are included. It may be derived from a group-containing monomer. The hydrophilic group is not particularly limited and may be a dissociable group or a nonionic hydrophilic group. The hydrophilic group is preferably a dissociable group and more preferably an anionic dissociative group from the viewpoint of promoting self-dispersion and the stability of the formed emulsified or dispersed state. Examples of the dissociable group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among these, a carboxyl group is preferable from the viewpoint of fixability when an ink composition is formed.
　親水性基含有モノマーは、自己分散性と凝集性の観点から、解離性基含有モノマーであることが好ましく、解離性基とエチレン性不飽和結合とを有する解離性基含有モノマーであることが好ましい。解離性基含有モノマーとしては、例えば、不飽和カルボン酸モノマー、不飽和スルホン酸モノマー、不飽和リン酸モノマー等が挙げられる。 The hydrophilic group-containing monomer is preferably a dissociable group-containing monomer from the viewpoint of self-dispersibility and aggregability, and is preferably a dissociable group-containing monomer having a dissociable group and an ethylenically unsaturated bond. . Examples of the dissociable group-containing monomer include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.
　上記不飽和カルボン酸モノマーの具体例としては、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、シトラコン酸、２－メタクリロイルオキシエチルコハク酸等が挙げられる。また、上記不飽和スルホン酸モノマー及び上記不飽和リン酸モノマーの具体例については、特開２００１－１６２６９２号公報の段落番号［００６３］～［００６５］に記載されている。
　上記解離性基含有モノマーの中では、分散安定性、吐出安定性の観点から、不飽和カルボン酸モノマーが好ましく、アクリル系モノマーがより好ましく、特にはアクリル酸及びメタクリル酸が好ましい。 Specific examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxyethyl succinic acid. Specific examples of the unsaturated sulfonic acid monomer and the unsaturated phosphoric acid monomer are described in paragraph numbers [0063] to [0065] of JP-A No. 2001-162692.
Among the dissociable group-containing monomers, from the viewpoint of dispersion stability and ejection stability, unsaturated carboxylic acid monomers are preferable, acrylic monomers are more preferable, and acrylic acid and methacrylic acid are particularly preferable.
　自己分散性樹脂の粒子は、自己分散性と処理液を用いて画像形成する際の処理液接触時における凝集速度の観点から、カルボキシル基を有するポリマーを含むことが好ましく、カルボキシル基を有し、酸価が２５～１００ｍｇＫＯＨ／ｇであるポリマーを含むことがより好ましい。更に、上記酸価は、自己分散性の観点から、３０～９０ｍｇＫＯＨ／ｇであることがより好ましく、３５～６５ｍｇＫＯＨ／ｇであることが特に好ましい。特に、酸価は、２５ｍｇＫＯＨ／ｇ以上であると、自己分散性の安定性が良好になり、１００ｍｇＫＯＨ／ｇ以下であると凝集性が向上する。 The self-dispersing resin particles preferably contain a polymer having a carboxyl group, from the viewpoint of self-dispersibility and the aggregation rate at the time of contact with the processing liquid when forming an image using the processing liquid, and having a carboxyl group, More preferably, it contains a polymer having an acid value of 25 to 100 mgKOH / g. Further, the acid value is more preferably from 30 to 90 mgKOH / g, particularly preferably from 35 to 65 mgKOH / g, from the viewpoint of self-dispersibility. In particular, when the acid value is 25 mgKOH / g or more, the stability of self-dispersibility is good, and when it is 100 mgKOH / g or less, the cohesiveness is improved.
　上記芳香族基含有モノマーは、芳香族基と重合性基とを含む化合物であれば特に制限はない。上記芳香族基は芳香族炭化水素に由来する基であっても、芳香族複素環に由来する基であってもよい。本発明においては水性媒体中での粒子形状安定性の観点から、芳香族炭化水素に由来する芳香族基であることが好ましい。
　また、上記重合性基は、縮重合性の重合性基でも付加重合性の重合性基でもよい。本発明においては水性媒体中での粒子形状安定性の観点から、付加重合性の重合性基であることが好ましく、エチレン性不飽和結合を含む基であることがより好ましい。 The aromatic group-containing monomer is not particularly limited as long as it is a compound containing an aromatic group and a polymerizable group. The aromatic group may be a group derived from an aromatic hydrocarbon or a group derived from an aromatic heterocyclic ring. In the present invention, an aromatic group derived from an aromatic hydrocarbon is preferable from the viewpoint of particle shape stability in an aqueous medium.
The polymerizable group may be a polycondensable polymerizable group or an addition polymerizable polymerizable group. In the present invention, from the viewpoint of particle shape stability in an aqueous medium, an addition polymerizable group is preferable, and a group containing an ethylenically unsaturated bond is more preferable.
　芳香族基含有モノマーは、芳香族炭化水素に由来する芳香族基とエチレン性不飽和結合とを有するモノマーであることが好ましい。芳香族基含有モノマーは、１種単独でも、２種以上を組み合わせて用いてもよい。芳香族基含有モノマーとしては、例えば、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、スチレン系モノマー等が挙げられる。中でも、ポリマー鎖の親水性と疎水性のバランスとインク定着性の観点から、芳香族基含有（メタ）アクリレートモノマーが好ましく、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、及びフェニル（メタ）アクリレートから選ばれる少なくとも１種がより好ましく、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレートが更に好ましい。
　なお、「（メタ）アクリレート」は、アクリレート又はメタクリレートを意味する。 The aromatic group-containing monomer is preferably a monomer having an aromatic group derived from an aromatic hydrocarbon and an ethylenically unsaturated bond. The aromatic group-containing monomer may be used alone or in combination of two or more. Examples of the aromatic group-containing monomer include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and a styrene monomer. Of these, aromatic group-containing (meth) acrylate monomers are preferred from the viewpoint of the balance between the hydrophilicity and hydrophobicity of the polymer chain and the ink fixability, and include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth). At least one selected from acrylates is more preferable, and phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are more preferable.
“(Meth) acrylate” means acrylate or methacrylate.
　上記環状脂肪族基含有モノマーは、環状脂肪族炭化水素に由来する環状脂肪族基とエチレン性不飽和結合とを有するモノマーであることが好ましく、環状脂肪族基含有（メタ）アクリレートモノマー（以下、脂環式（メタ）アクリレートということがある）がより好ましい。
　脂環式（メタ）アクリレートとは、（メタ）アクリル酸に由来する構造部位と、アルコールに由来する構造部位とを含み、アルコールに由来する構造部位に、無置換又は置換された脂環式炭化水素基（環状脂肪族基）を少なくとも１つ含む構造を有しているものである。なお、上記脂環式炭化水素基は、アルコールに由来する構造部位そのものであっても、連結基を介してアルコールに由来する構造部位に結合していてもよい。 The cycloaliphatic group-containing monomer is preferably a monomer having a cycloaliphatic group derived from a cycloaliphatic hydrocarbon and an ethylenically unsaturated bond, and a cycloaliphatic group-containing (meth) acrylate monomer (hereinafter, An alicyclic (meth) acrylate is sometimes preferred.
The alicyclic (meth) acrylate includes a structural site derived from (meth) acrylic acid and a structural site derived from alcohol, and the structural site derived from alcohol is unsubstituted or substituted. It has a structure containing at least one hydrogen group (cycloaliphatic group). In addition, the said alicyclic hydrocarbon group may be couple | bonded with the structural site | part derived from alcohol through the coupling group, even if it is the structural site | part derived from alcohol itself.
　脂環式炭化水素基としては、環状の非芳香族炭化水素基を含むものであれば特に限定はなく、単環式炭化水素基、２環式炭化水素基、３環式以上の多環式炭化水素基が挙げられる。脂環式炭化水素基としては、例えば、シクロペンチル基、シクロヘキシル基等のシクロアルキル基や、シクロアルケニル基、ビシクロヘキシル基、ノルボルニル基、イソボルニル基、ジシクロペンタニル基、ジシクロペンテニル基、アダマンチル基、デカヒドロナフタレニル基、ペルヒドロフルオレニル基、トリシクロ［５．２．１．０２，６]デカニル基、及びビシクロ［４.３.０］ノナン等を挙げることができる。上記脂環式炭化水素基は、更に置換基を有してもよい。脂環式炭化水素基は、更に縮合環を形成していてもよい。本発明における脂環式炭化水素基としては、粘度や溶解性の観点から、脂環式炭化水素基部分の炭素数が５～２０であることが好ましい。 The alicyclic hydrocarbon group is not particularly limited as long as it contains a cyclic non-aromatic hydrocarbon group, and is a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or more polycyclic group. A hydrocarbon group is mentioned. Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkenyl group, a bicyclohexyl group, a norbornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group. , Decahydronaphthalenyl group, perhydrofluorenyl group, tricyclo [5.2.1.0 2,6 ] decanyl group, and bicyclo [4.3.0] nonane. The alicyclic hydrocarbon group may further have a substituent. The alicyclic hydrocarbon group may further form a condensed ring. The alicyclic hydrocarbon group in the present invention preferably has 5 to 20 carbon atoms in the alicyclic hydrocarbon group portion from the viewpoint of viscosity and solubility.
　脂環式（メタ）アクリレートの具体例を以下に示すが、本発明はこれらに限定されるものではない。
　単環式（メタ）アクリレートとしては、シクロプロピル（メタ）アクリレート、シクロブチル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、シクロヘプチル（メタ）アクリレート、シクロオクチル（メタ）アクリレート、シクロノニル（メタ）アクリレート、シクロデシル（メタ）アクリレート等のシクロアルキル基の炭素数が３～１０のシクロアルキル（メタ）アクリレート等が挙げられる。２環式（メタ）アクリレートとしては、イソボルニル（メタ）アクリレート、ノルボルニル（メタ）アクリレート等が挙げられる。３環式（メタ）アクリレートとしては、アダマンチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート等が挙げられる。これらは、それぞれ単独で又は２種以上を混合して用いることができる。 Specific examples of the alicyclic (meth) acrylate are shown below, but the present invention is not limited thereto.
Monocyclic (meth) acrylates include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, and cyclononyl. Examples thereof include cycloalkyl (meth) acrylates having 3 to 10 carbon atoms in the cycloalkyl group such as (meth) acrylate and cyclodecyl (meth) acrylate. Examples of the bicyclic (meth) acrylate include isobornyl (meth) acrylate and norbornyl (meth) acrylate. Examples of the tricyclic (meth) acrylate include adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in admixture of two or more.
　これらのうち、自己分散性ポリマー粒子の分散安定性と定着性、ブロッキング耐性の観点から、２環式又は３環式以上の（メタ）アクリレートであることが好ましく、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、及びジシクロペンタニル（メタ）アクリレートから選ばれる少なくとも１種であることがより好ましい。 Among these, from the viewpoints of dispersion stability and fixing properties of the self-dispersing polymer particles and blocking resistance, a bicyclic or tricyclic or higher (meth) acrylate is preferable, and isobornyl (meth) acrylate, adamantyl ( More preferably, it is at least one selected from (meth) acrylate and dicyclopentanyl (meth) acrylate.
　自己分散性樹脂は、（メタ）アクリレートモノマーに由来する構成単位を含むアクリル系樹脂が好ましく、芳香族基含有（メタ）アクリレートモノマー又は脂環式（メタ）アクリレートに由来する構成単位を含むアクリル系樹脂が好ましく、更には、芳香族基含有（メタ）アクリレートモノマー又は脂環式（メタ）アクリレートに由来する構成単位を含み、その含有量が１０～９５質量％であることが好ましい。芳香族基含有（メタ）アクリレートモノマー又は脂環式（メタ）アクリレートの含有量が１０～９５質量％であることで、自己乳化又は分散状態の安定性が向上し、更にインク粘度の上昇を抑制することができる。
　自己分散状態の安定性、芳香環同士の疎水性相互作用による水性媒体中での粒子形状の安定化、粒子の適度な疎水化による水溶性成分量の低下の観点から、１５～９０質量％であることがより好ましく、１５～８０質量％であることがより好ましく、２５～７０質量％であることが特に好ましい。 The self-dispersing resin is preferably an acrylic resin containing a structural unit derived from a (meth) acrylate monomer, and an acrylic resin containing a structural unit derived from an aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate. A resin is preferable, and further, it contains a structural unit derived from an aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate, and its content is preferably 10 to 95% by mass. When the content of the aromatic group-containing (meth) acrylate monomer or alicyclic (meth) acrylate is 10 to 95% by mass, the stability of the self-emulsification or dispersion state is improved, and the increase in ink viscosity is further suppressed. can do.
From the viewpoint of the stability of the self-dispersing state, the stabilization of the particle shape in the aqueous medium due to the hydrophobic interaction between the aromatic rings, and the reduction in the amount of water-soluble components due to the appropriate hydrophobicity of the particles, 15 to 90% by mass More preferably, it is more preferably 15 to 80% by mass, and particularly preferably 25 to 70% by mass.
　自己分散性樹脂は、例えば、芳香族基含有モノマー又は環状脂肪族基含有モノマー（好ましくは脂環式（メタ）アクリレート）に由来する構成単位と、解離性基含有モノマーに由来する構成単位とを用いて構成することができる。更に、必要に応じて、その他の構成単位を更に含んでもよい。 The self-dispersing resin includes, for example, a structural unit derived from an aromatic group-containing monomer or a cycloaliphatic group-containing monomer (preferably an alicyclic (meth) acrylate) and a structural unit derived from a dissociable group-containing monomer. Can be configured. Furthermore, other structural units may be further included as necessary.
　上記その他の構成単位を形成するモノマーとしては、上記芳香族基含有モノマーと解離性基含有モノマーと共重合可能なモノマーであれば特に制限はない。中でも、ポリマー骨格の柔軟性やガラス転移温度（Ｔｇ）制御の容易さの観点から、アルキル基含有モノマー（例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート）であることが好ましい。 The monomer forming the other structural unit is not particularly limited as long as it is a monomer copolymerizable with the aromatic group-containing monomer and the dissociable group-containing monomer. Among them, from the viewpoint of flexibility of the polymer skeleton and easy control of the glass transition temperature (Tg), an alkyl group-containing monomer (for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl) (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate and other alkyl (meth) acrylates) preferable.
　自己分散性樹脂の粒子を構成する水不溶性ポリマーの分子量としては、重量平均分子量で３０００～２０万であることが好ましく、５０００～１５万であることがより好ましく、１００００～１０万であることが更に好ましい。重量平均分子量を３０００以上とすることで水溶性成分量を効果的に抑制することができる。また、重量平均分子量を２０万以下とすることで、自己分散安定性を高めることができる。
　なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）で測定される。ＧＰＣの詳細については、既述した通りである。 The molecular weight of the water-insoluble polymer constituting the self-dispersing resin particles is preferably from 3,000 to 200,000, more preferably from 5,000 to 150,000, and more preferably from 10,000 to 100,000. Further preferred. By setting the weight average molecular weight to 3000 or more, the amount of water-soluble components can be effectively suppressed. Moreover, self-dispersion stability can be improved by making a weight average molecular weight into 200,000 or less.
The weight average molecular weight is measured by gel permeation chromatography (GPC). The details of GPC are as described above.
　自己分散性樹脂の粒子を構成する水不溶性ポリマーは、ポリマーの親疎水性制御の観点から、芳香族基含有（メタ）アクリレートモノマーに由来する構造単位あるいは環状脂肪族基含有モノマー（好ましくは脂環式（メタ）アクリレート）を共重合比率として自己分散性ポリマー粒子の全質量の１５～８０質量％を含むことが好ましい。
　更には、水不溶性ポリマーは、ポリマーの親疎水性制御の観点から、芳香族基含有（メタ）アクリレートモノマーに由来する構成単位（好ましくは、フェノキシエチル（メタ）アクリレート由来の構造単位及び／又はベンジル（メタ）アクリレート由来の構造単位）又は脂環式（メタ）アクリレートに由来する構成単位（好ましくは、イソボルニル（メタ）アクリレート由来の構造単位及び／又はアダマンチル（メタ）アクリレート由来の構造単位及び／又はジシクロペンタニル（メタ）アクリレート）由来の構造単位）を共重合比率として１５～８０質量％と、カルボキシル基含有モノマーに由来する構成単位と、アルキル基含有モノマーに由来する構成単位（好ましくは（メタ）アクリル酸の（炭素数１～４の）アルキルエステルに由来する構造単位）とを含むことが好ましい。 The water-insoluble polymer constituting the self-dispersing resin particles is a structural unit derived from an aromatic group-containing (meth) acrylate monomer or a cyclic aliphatic group-containing monomer (preferably an alicyclic group) from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer. (Meth) acrylate) is preferably contained in a copolymerization ratio of 15 to 80% by mass of the total mass of the self-dispersing polymer particles.
Furthermore, the water-insoluble polymer is a structural unit derived from an aromatic group-containing (meth) acrylate monomer (preferably a structural unit derived from phenoxyethyl (meth) acrylate and / or benzyl (from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer). Structural units derived from (meth) acrylates) or structural units derived from alicyclic (meth) acrylates (preferably structural units derived from isobornyl (meth) acrylates and / or structural units derived from adamantyl (meth) acrylates and / or di). Structural unit derived from cyclopentanyl (meth) acrylate) as a copolymerization ratio of 15 to 80% by mass, a structural unit derived from a carboxyl group-containing monomer, and a structural unit derived from an alkyl group-containing monomer (preferably (meta ) Derived from alkyl ester (1-4 carbon atoms) of acrylic acid Preferably includes a structural unit) and that.
　ポリマー粒子を形成する水不溶性樹脂の具体例としては、フェノキシエチルアクリレート／メチルメタクリレート／アクリル酸共重合体（５０／４５／５）、フェノキシエチルアクリレート／ベンジルメタクリレート／イソブチルメタクリレート／メタクリル酸共重合体（３０／３５／２９／６）、フェノキシエチルメタクリレート／イソブチルメタクリレート／メタクリル酸共重合体（５０／４４／６）、フェノキシエチルアクリレート／メチルメタクリレート／エチルアクリレート／アクリル酸共重合体（３０／５５／１０／５）、ベンジルメタクリレート／イソブチルメタクリレート／メタクリル酸共重合体（３５／５９／６）、スチレン／フェノキシエチルアクリレート／メチルメタクリレート／アクリル酸共重合体（１０／５０／３５／５）、ベンジルアクリレート／メチルメタクリレート／アクリル酸共重合体（５５／４０／５）、フェノキシエチルメタクリレート／ベンジルアクリレート／メタクリル酸共重合体（４５／４７／８）、スチレン／フェノキシエチルアクリレート／ブチルメタクリレート／アクリル酸共重合体（５／４８／４０／７）、ベンジルメタクリレート／イソブチルメタクリレート／シクロヘキシルメタクリレート／メタクリル酸共重合体（３５／３０／３０／５）、フェノキシエチルアクリレート／メチルメタクリレート／ブチルアクリレート／メタクリル酸共重合体（１２／５０／３０／８）、ベンジルアクリレート／イソブチルメタクリレート／アクリル酸共重合体（９３／２／５）、メチルメタクリレート／メトキシエチルアクリレート／ベンジルメタクリレート／アクリル酸共重合体（４４／１５／３５／６）、スチレン／ブチルアクリレート／アクリル酸共重合体（６２／３５／３）、メチルメタクリレート／フェノキシエチルアクリレート／アクリル酸共重合体（４５／５１／４）、メチルメタクリレート／イソボルニルメタクリレート／メタクリル酸共重合体（２０／７２／８）、メチルメタクリレート／イソボルニルメタクリレート／メタクリル酸共重合体（４０／５２／８）、メチルメタクリレート／イソボルニルメタクリレート／メタクリル酸共重合体（４８／４２／１０）、メチルメタクリレート／イソボルニルメタクリレート／ジシクロペンタニルメタクリレート／メタクリル酸共重合体（２０／６２／１０／８）、メチルメタクリレート／ジシクロペンタニルメタクリレート／メタクリル酸共重合体（２０／７２／８）等が挙げられる。なお、括弧内は、共重合成分の質量比を表す。 Specific examples of the water-insoluble resin forming the polymer particles include phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (50/45/5), phenoxyethyl acrylate / benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer ( 30/35/29/6), phenoxyethyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (50/44/6), phenoxyethyl acrylate / methyl methacrylate / ethyl acrylate / acrylic acid copolymer (30/55/10 / 5), benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (35/59/6), styrene / phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (10/50 35/5), benzyl acrylate / methyl methacrylate / acrylic acid copolymer (55/40/5), phenoxyethyl methacrylate / benzyl acrylate / methacrylic acid copolymer (45/47/8), styrene / phenoxyethyl acrylate / Butyl methacrylate / acrylic acid copolymer (5/48/40/7), benzyl methacrylate / isobutyl methacrylate / cyclohexyl methacrylate / methacrylic acid copolymer (35/30/30/5), phenoxyethyl acrylate / methyl methacrylate / butyl Acrylate / methacrylic acid copolymer (12/50/30/8), benzyl acrylate / isobutyl methacrylate / acrylic acid copolymer (93/2/5), methyl methacrylate / methoxyethyl acrylate / Benzyl methacrylate / acrylic acid copolymer (44/15/35/6), styrene / butyl acrylate / acrylic acid copolymer (62/35/3), methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/51/4), methyl methacrylate / isobornyl methacrylate / methacrylic acid copolymer (20/72/8), methyl methacrylate / isobornyl methacrylate / methacrylic acid copolymer (40/52/8), Methyl methacrylate / isobornyl methacrylate / methacrylic acid copolymer (48/42/10), methyl methacrylate / isobornyl methacrylate / dicyclopentanyl methacrylate / methacrylic acid copolymer (20/62/10/8), Methyl methacrylate / dicyclopen Tanyl methacrylate / methacrylic acid copolymer (20/72/8) and the like. The values in parentheses represent the mass ratio of the copolymer component.
　ポリマー粒子を形成する不溶性樹脂は、有機溶剤中で合成されたポリマーを含み、該ポリマーはアニオン性基（例えば、カルボキシル基）を有し、該ポリマーのアニオン性基（例えば、カルボキシル基）の一部又は全部は中和され、水を連続相とするポリマー分散物（分散体）として調製されたものであることが好ましい。すなわち、水不溶性ポリマー粒子の製造は、有機溶剤中でポリマーを合成する工程と、上記ポリマーのアニオン性基（例えば、カルボキシル基）の少なくとも一部が中和された水性分散物とする分散工程とを設けて行なうことが好ましい。上記分散工程は、次の工程（1）及び工程（2）を含むことが好ましい。
・工程（1）：ポリマー（水不溶性ポリマー）、有機溶剤、中和剤、及び水性媒体を含有する混合物を、攪拌する工程
・工程（2）：上記混合物から上記有機溶剤を除去する工程 The insoluble resin forming the polymer particles includes a polymer synthesized in an organic solvent, and the polymer has an anionic group (for example, carboxyl group), and one of the anionic groups (for example, carboxyl group) of the polymer. Part or all of them are preferably neutralized and prepared as a polymer dispersion (dispersion) having water as a continuous phase. That is, the production of water-insoluble polymer particles includes a step of synthesizing a polymer in an organic solvent, and a dispersion step of preparing an aqueous dispersion in which at least a part of the anionic group (for example, carboxyl group) of the polymer is neutralized. It is preferable to carry out. The dispersion step preferably includes the following step (1) and step (2).
-Step (1): Step of stirring a mixture containing a polymer (water-insoluble polymer), an organic solvent, a neutralizing agent, and an aqueous medium-Step (2): Step of removing the organic solvent from the mixture
　上記工程（1）は、まずポリマー（水不溶性ポリマー）を有機溶剤に溶解させ、次に中和剤と水性媒体を徐々に加えて混合、攪拌して分散体を得る処理であることが好ましい。このように、有機溶剤中に溶解した水不溶性ポリマー溶液中に中和剤と水性媒体を添加することで、強いせん断力を必要とせずに、より保存安定性の高い粒径の自己分散性ポリマー粒子を得ることができる。混合物の攪拌方法に特に制限はなく、一般に用いられる混合攪拌装置や、必要に応じて超音波分散機や高圧ホモジナイザー等の分散機を用いることができる。また、上記工程（2）においては、上記工程（1）で得られた分散体から、減圧蒸留等の常法により有機溶剤を留去して水系へと転相することで自己分散性ポリマー粒子の水性分散物を得ることができる。得られた水性分散物中の有機溶剤は実質的に除去されており、有機溶剤の量は、好ましくは０．２質量％以下、更に好ましくは０．１質量％以下である。 The step (1) is preferably a treatment in which a polymer (water-insoluble polymer) is first dissolved in an organic solvent, and then a neutralizer and an aqueous medium are gradually added, mixed and stirred to obtain a dispersion. Thus, by adding a neutralizing agent and an aqueous medium to a water-insoluble polymer solution dissolved in an organic solvent, a self-dispersing polymer having a particle size with higher storage stability without requiring strong shearing force. Particles can be obtained. There is no restriction | limiting in particular in the stirring method of a mixture, Dispersing machines, such as a generally used mixing stirring apparatus and an ultrasonic disperser, a high-pressure homogenizer, can be used as needed. In the step (2), the organic solvent is distilled off from the dispersion obtained in the step (1) by a conventional method such as distillation under reduced pressure, and the self-dispersing polymer particles are phase-shifted into an aqueous system. An aqueous dispersion of can be obtained. The organic solvent in the obtained aqueous dispersion has been substantially removed, and the amount of the organic solvent is preferably 0.2% by mass or less, more preferably 0.1% by mass or less.
　上記有機溶剤としては、アルコール系溶剤、ケトン系溶剤及びエーテル系溶剤が好ましく挙げられる。有機溶剤としては、特開２０１０－１８８６６１号公報の段落００５９に例示された有機溶剤を用いることができる。
　上記中和剤としては、特開２０１０－１８８６６１号公報の段落００６０～００６１に例示された中和剤を用いることができる。 Preferred examples of the organic solvent include alcohol solvents, ketone solvents, and ether solvents. As the organic solvent, organic solvents exemplified in paragraph 0059 of JP 2010-188661 A can be used.
As the neutralizing agent, neutralizing agents exemplified in paragraphs 0060 to 0061 of JP 2010-188661 A can be used.
　自己分散性樹脂の粒子の平均粒子径は、体積平均粒子径で１０～４００ｎｍの範囲が好ましい。また、自己分散性樹脂の粒子の粒径分布に関しては、特に制限はなく、広い粒径分布を持つもの又は単分散の粒径分布を持つもののいずれでもよい。また、水不溶性粒子を２種以上混合して使用してもよい。 The average particle size of the self-dispersing resin particles is preferably in the range of 10 to 400 nm in terms of volume average particle size. Further, the particle size distribution of the self-dispersing resin particles is not particularly limited, and may be either a wide particle size distribution or a monodispersed particle size distribution. Further, two or more water-insoluble particles may be mixed and used.
　ポリマー粒子のインク組成物中における含有量としては、インク組成物の全量（質量基準）に対して、０．５～１０質量％が好ましく、１～９質量％がより好ましい。ポリマー粒子の含有量が０．５質量％以上であると、画像の耐擦過性が向上する。また、ポリマー粒子の含有量が１０質量％以下であると、インク組成物を調整したときに長期に亘る吐出安定性の点で有利である。 The content of the polymer particles in the ink composition is preferably 0.5 to 10% by mass and more preferably 1 to 9% by mass with respect to the total amount (mass basis) of the ink composition. When the content of the polymer particles is 0.5% by mass or more, the scratch resistance of the image is improved. Moreover, when the content of the polymer particles is 10% by mass or less, it is advantageous in terms of ejection stability over a long period of time when the ink composition is prepared.
（水）
　本発明におけるインク組成物は、水を用いて構成することができる。水の量には、特に制限はないが、安定性及び吐出信頼性の確保の点で、好ましくは１０質量％以上９９質量％以下である。 (water)
The ink composition in the present invention can be constituted using water. Although there is no restriction | limiting in particular in the quantity of water, Preferably it is 10 to 99 mass% from the point of ensuring stability and discharge reliability.
（尿素又はその誘導体）
　本発明のインク組成物は、尿素又はその誘導体を含有することが好ましい。尿素及びその誘導体によれば、顔料を含むインク組成物が付着した場合のワイピング等によるクリーニング性が向上する。特に上記ポリマー粒子を含有する場合に、乾燥固化したときの拭き取り性（ワイピング性）が改善される。 (Urea or its derivatives)
The ink composition of the present invention preferably contains urea or a derivative thereof. According to urea and its derivatives, the cleaning property by wiping or the like when an ink composition containing a pigment adheres is improved. In particular, when the polymer particles are contained, the wiping property (wiping property) when dried and solidified is improved.
　尿素の誘導体の例としては、尿素の窒素上の水素をアルキル基もしくはアルカノールで置換した化合物、チオ尿素、チオ尿素の窒素上の水素をアルキル基もしくはアルカノールで置換した化合物等が挙げられ、具体的には、Ｎ，Ｎ－ジメチル尿素、チオ尿素、エチレン尿素、ヒドロキシエチル尿素、ヒドロキシブチル尿素、エチレンチオ尿素、ジエチルチオ尿素等が挙げられる。 Examples of urea derivatives include compounds in which the hydrogen on the nitrogen of urea is substituted with an alkyl group or alkanol, thiourea, compounds in which the hydrogen on the nitrogen of thiourea is substituted with an alkyl group or alkanol, and the like. N, N-dimethylurea, thiourea, ethyleneurea, hydroxyethylurea, hydroxybutylurea, ethylenethiourea, diethylthiourea and the like.
　尿素及びその誘導体のインク組成物中における含有量としては、インク組成物の全質量に対して、１．０質量％以上２０．０質量％以下が好ましく、２．０質量％以上１５．０質量％以下がより好ましい。
　尿素及びその誘導体の含有量が１．０質量％以上であると、インクが付着した場合により拭き取り易くなり、メンテナンス性が向上する。また、尿素及びその誘導体の含有量が２０．０質量％以下であると、画像中に含まれる尿素及びその誘導体の吸湿によるベタツキ防止、ブロッキング防止の点で有利である。 The content of urea and its derivative in the ink composition is preferably 1.0% by mass or more and 20.0% by mass or less, and 2.0% by mass or more and 15.0% by mass with respect to the total mass of the ink composition. % Or less is more preferable.
When the content of urea and its derivative is 1.0% by mass or more, it becomes easier to wipe off when the ink adheres, and the maintainability is improved. Further, when the content of urea and its derivative is 20.0% by mass or less, it is advantageous in terms of prevention of stickiness and blocking due to moisture absorption of urea and its derivative contained in the image.
（他の成分）
　本発明におけるインク組成物は、上記成分のほか、必要に応じて、その他の成分を含むことができる。その他の成分としては、例えば、界面活性剤、紫外線吸収剤、褪色防止剤、防黴剤、ｐＨ調整剤、防錆剤、酸化防止剤、乳化安定剤、防腐剤、消泡剤、粘度調整剤、分散安定剤、キレート剤等の公知の添加剤が挙げられる。 (Other ingredients)
The ink composition in the invention may contain other components in addition to the above components, if necessary. Other components include, for example, surfactants, ultraviolet absorbers, antifading agents, antifungal agents, pH adjusters, rust inhibitors, antioxidants, emulsion stabilizers, antiseptics, antifoaming agents, viscosity modifiers. And known additives such as dispersion stabilizers and chelating agents.
　本発明におけるインク組成物のｐＨは、特に限定されるものではないが、インク組成物中に含まれる色材の凝集を防ぎ、かつ洗浄性を高める観点から、２５℃におけるｐＨはｐＨ６．５～１２の範囲が好ましく、ｐＨ７～１０の範囲がより好ましい。インク組成物のｐＨを上記範囲に調整するために、必要に応じて上述の水溶性塩基性物質等のｐＨ調整剤を使用することができる。 The pH of the ink composition in the present invention is not particularly limited, but the pH at 25 ° C. is pH 6.5 to from the viewpoint of preventing aggregation of the coloring material contained in the ink composition and improving the cleaning property. The range of 12 is preferable, and the range of pH 7 to 10 is more preferable. In order to adjust the pH of the ink composition to the above range, a pH adjuster such as the above-mentioned water-soluble basic substance can be used as necessary.
　本発明のインクセットは、顔料を含むインク組成物と既述の本発明のメンテナンス液とを設けて構成される。メンテナンス液の構成は、既述の本発明のメンテナンス液と同義であり、好ましい例も同様である。 The ink set of the present invention is configured by providing an ink composition containing a pigment and the above-described maintenance liquid of the present invention. The structure of the maintenance liquid is synonymous with the maintenance liquid of the present invention described above, and the preferred examples are also the same.
　本発明のインクジェット記録用メンテナンス液及びインクセットは、インクジェット記録に用いられるものであり、具体的には、インクジェット記録用のインクにエネルギーを供与して、公知の受像材料（例えば、普通紙、樹脂コート紙、インクジェット専用紙、フイルム、電子写真共用紙、布帛、ガラス、金属、陶磁器等）に画像を記録する場合に用いられる。 The maintenance liquid and ink set for ink jet recording of the present invention are used for ink jet recording. Specifically, energy is given to ink for ink jet recording, and a known image receiving material (for example, plain paper, resin) is used. (Coated paper, inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc.).
＜画像形成方法＞
　本発明の画像形成方法は、既述の本発明のインクジェット記録用インクセットが用いられ、インク組成物をインクジェット記録用ヘッドから吐出することで、インク組成物を記録媒体に付与するインク付与工程と、インクジェット記録用ヘッドに付着したインク組成物をインクジェット記録用メンテナンス液により除去するインク除去工程とを有する。本発明の画像形成方法は、更に、インク組成物中の成分を凝集させる凝集成分を含有する処理液を記録媒体に付与する処理液付与工程を有してもよい。 <Image forming method>
The image forming method of the present invention uses the ink set for ink jet recording of the present invention described above, and an ink application process for applying the ink composition to a recording medium by discharging the ink composition from the head for ink jet recording. And an ink removing step for removing the ink composition adhering to the ink jet recording head with a maintenance liquid for ink jet recording. The image forming method of the present invention may further include a treatment liquid applying step of applying a treatment liquid containing an aggregating component for aggregating the components in the ink composition to the recording medium.
　本発明の画像形成方法は、本発明のインクジェット記録用メンテナンス液を用いることで、既述のように、顔料及びポリマー粒子を含むためにインク吐出ヘッドの表面に付着しやすく、乾燥後には溶解、除去し難いインク、特に乾燥により固形化したインク固形物の溶解性に優れる。したがって、長期に亘り安定した画像形成性が保持される。これにより、洗浄後ふき取る等の過程で、例えばミスト状の微粒のインクが乾燥固化したようなインク固化物によって、吐出孔が閉塞されたり、吐出孔付近に堆積物が発生する等の現象が防止される。 As described above, the image forming method of the present invention uses the maintenance liquid for inkjet recording of the present invention, so that it easily adheres to the surface of the ink ejection head because it contains pigments and polymer particles, and dissolves after drying. Excellent solubility of ink that is difficult to remove, especially ink solidified by drying. Therefore, stable image formability is maintained over a long period of time. As a result, in the process of wiping after cleaning, for example, the phenomenon that the discharge holes are blocked or deposits are generated in the vicinity of the discharge holes due to ink solidified, such as mist-like fine particles of ink dried and solidified, is prevented. Is done.
－インク付与工程－
　本発明におけるインク付与工程は、インク組成物をインクジェット記録用ヘッドから吐出することで、インク組成物を記録媒体に付与し、記録媒体上に画像形成する。本工程では、記録媒体上にインク組成物を付与でき、所望の可視画像を形成できる。なお、インク組成物の詳細については既述の通りである。 -Ink application process-
In the ink application process of the present invention, the ink composition is ejected from an ink jet recording head, whereby the ink composition is applied to the recording medium, and an image is formed on the recording medium. In this step, the ink composition can be applied on the recording medium, and a desired visible image can be formed. The details of the ink composition are as described above.
　インクジェット法は、特に制限はなく、公知の方式、例えば、静電誘引力を利用してインクを吐出させる電荷制御方式、ピエゾ素子の振動圧力を利用するドロップオンデマンド方式（圧力パルス方式）、電気信号を音響ビームに変えインクに照射して放射圧を利用してインクを吐出させる音響インクジェット方式、及びインクを加熱して気泡を形成し、生じた圧力を利用するサーマルインクジェット（バブルジェット（登録商標））方式等のいずれであってもよい。インクジェット法としては、特に、特開昭５４－５９９３６号公報に記載の方法で、熱エネルギーの作用を受けたインクが急激な体積変化を生じ、この状態変化による作用力によって、インクをノズルから吐出させるインクジェット法を有効に利用することができる。
　なお、上記インクジェット法には、フォトインクと称する濃度の低いインクを小さい体積で多数射出する方式、実質的に同じ色相で濃度の異なる複数のインクを用いて画質を改良する方式や無色透明のインクを用いる方式が含まれる。 The inkjet method is not particularly limited, and is a known method, for example, a charge control method that discharges ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an electric method An acoustic ink jet system that converts a signal into an acoustic beam, irradiates the ink with ink and ejects the ink using radiation pressure, and a thermal ink jet (bubble jet (registered trademark)) that heats the ink to form bubbles and uses the generated pressure. )) Any method may be used. As an ink jet method, in particular, the method described in Japanese Patent Laid-Open No. Sho 54-59936 causes a sudden change in volume of the ink subjected to the action of thermal energy, and the ink is ejected from the nozzle by the action force caused by this state change. Ink jet method can be used effectively.
The ink jet method includes a method of ejecting many low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method using is included.
　インクジェット法で用いるインクジェットヘッドは、オンデマンド方式でもコンティニュアス方式でも構わない。また、吐出方式としては、電気－機械変換方式（例えば、シングルキャビティー型、ダブルキャビティー型、ベンダー型、ピストン型、シェアーモード型、シェアードウォール型等）、電気－熱変換方式（例えば、サーマルインクジェット型、バブルジェット（登録商標）型等）、静電吸引方式（例えば、電界制御型、スリットジェット型等）及び放電方式（例えば、スパークジェット型等）等を具体的な例として挙げることができるが、いずれの吐出方式を用いてもよい。なお、上記インクジェット法により記録を行う際に使用するインクノズル等については特に制限はなく、目的に応じて、適宜選択することができる。 The inkjet head used in the inkjet method may be an on-demand method or a continuous method. Discharge methods include electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), and electro-thermal conversion methods (eg, thermal Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic attraction type (for example, an electric field control type, a slit jet type, etc.), a discharge type (for example, a spark jet type, etc.), and the like. However, any discharge method may be used. There are no particular restrictions on the ink nozzles used when recording by the inkjet method, and they can be appropriately selected according to the purpose.
　インクジェットヘッドとしては、単尺のシリアルヘッドを用い、ヘッドを記録媒体の幅方向に走査させながら記録を行なうシャトル方式と、記録媒体の１辺の全域に対応して記録素子が配列されているラインヘッドを用いたライン方式とがある。ライン方式では、記録素子の配列方向と直交する方向に記録媒体を走査させることで記録媒体の全面に画像記録を行なうことができ、短尺ヘッドを走査するキャリッジ等の搬送系が不要となる。また、キャリッジの移動と記録媒体との複雑な走査制御が不要になり、記録媒体だけが移動するので、シャトル方式に比べて記録速度の高速化が実現できる。
　本発明の画像形成方法は、これらのいずれにも適用可能であるが、一般にダミージェットを行なわないライン方式に適用した場合に、吐出精度及び画像の耐擦過性の向上効果が大きい。 As an inkjet head, a single serial head is used, and a shuttle system that performs recording while scanning the head in the width direction of the recording medium, and a line in which recording elements are arranged corresponding to the entire area of one side of the recording medium. There is a line system using a head. In the line system, an image can be recorded on the entire surface of the recording medium by scanning the recording medium in a direction orthogonal to the arrangement direction of the recording elements, and a carriage system such as a carriage for scanning a short head is not necessary. Further, since complicated scanning control of the carriage movement and the recording medium is not required, and only the recording medium is moved, the recording speed can be increased as compared with the shuttle system.
The image forming method of the present invention can be applied to any of these, but generally, when applied to a line system that does not use a dummy jet, the effect of improving ejection accuracy and image scratch resistance is great.
　インク付与工程では、高精細印画の観点から、付与（打滴）されるインク滴の液滴量が１．５～３．０ｐＬであることが好ましく、１．５～２．５ｐＬであることがより好ましい。
　なお、インク滴の液滴量は、打滴するインク組成物に応じて、インクジェット法における吐出条件を適宜選択することで調整することができる。 In the ink application process, from the viewpoint of high-definition printing, the amount of ink droplets to be applied (droplet ejection) is preferably 1.5 to 3.0 pL, and more preferably 1.5 to 2.5 pL. More preferred.
The amount of ink droplets can be adjusted by appropriately selecting the ejection conditions in the ink jet method according to the ink composition to be ejected.
－インク除去工程－
　本発明におけるインク除去工程は、上記インク付与工程でインク組成物を吐出することにより、インクジェット記録用ヘッドに付着したインク組成物（例えば、乾燥により固形化したインク固形物）をインクジェット記録用メンテナンス液により除去する。本工程で用いるメンテナンス液の構成及び好ましい態様等の詳細については、既述した通りである。 -Ink removal process-
In the ink removing process of the present invention, the ink composition adhered to the ink jet recording head (for example, the ink solid material solidified by drying) is discharged from the ink applying process in the ink applying process to prepare an ink jet maintenance liquid. To remove. The details of the configuration and preferred embodiment of the maintenance liquid used in this step are as described above.
　インク除去工程では、ヘッドのノズル面からインク組成物を除去するために、ヘッド（例えば、ヘッド周辺及びインク流路等；以下、「ヘッド等」ともいう。）にメンテナンス液を付与する。メンテナンス液をヘッド等に付与することにより、インク組成物は溶解、膨潤等する。 In the ink removing process, in order to remove the ink composition from the nozzle surface of the head, a maintenance liquid is applied to the head (for example, the periphery of the head and the ink flow path; hereinafter, also referred to as “head etc.”). By applying the maintenance liquid to the head or the like, the ink composition dissolves or swells.
　メンテナンス液の付与は、例えば、インクジェット法による吐出、ローラを用いた塗布、噴霧等により行なえるが、例えば特開２０１１－７３２９５号や特開２０１１－７３３３９号等の公報に記載のように、水頭差を利用してメンテナンス液（洗浄液）塗布ユニット上にメンテナンス液柱を形成させ、そこをインクジェット記録用ヘッドが通過する際に、ヘッドとメンテナンス液塗布ユニット間に液膜が形成され、ヘッドにメンテナンス液が付与される方法が好ましい。 The maintenance liquid can be applied by, for example, ejection by an ink jet method, application using a roller, spraying, and the like. For example, as described in JP 2011-73295 A, JP 2011-73339 A, etc. Using the difference, a maintenance liquid column is formed on the maintenance liquid (cleaning liquid) application unit, and when the inkjet recording head passes there, a liquid film is formed between the head and the maintenance liquid application unit, and maintenance is performed on the head. A method in which a liquid is applied is preferred.
　また、メンテナンス液を付与する前又は後に、ブレードによる掻き取り、布や紙類での払拭により、インク組成物を除去することが好ましい。好ましい方法としては、メンテナンス液を付与後にワイパブレードを用いてノズル面を擦って（ワイピングして）インク組成物を掻き落とす方法、風圧やメンテナンス液等の液圧等によりインク組成物を取り除く方法、布や紙類でインク組成物を払拭する方法が挙げられ、特に布や紙類でインク組成物を払拭する方法が好ましい。常に新しい布で払拭する方法として、例えば特開２０１０－２４１１２７号公報により、払拭部材の交換頻度を低減し装置をコンパクトにする方法が開示されている。 Also, it is preferable to remove the ink composition by scraping with a blade or wiping with a cloth or paper before or after applying the maintenance liquid. As a preferred method, after the maintenance liquid is applied, the nozzle surface is rubbed with a wiper blade (wiping) and the ink composition is scraped off, the method of removing the ink composition by wind pressure, the liquid pressure of maintenance liquid, etc., A method of wiping the ink composition with a cloth or paper is exemplified, and a method of wiping the ink composition with a cloth or paper is particularly preferable. As a method of always wiping with a new cloth, for example, Japanese Patent Application Laid-Open No. 2010-241127 discloses a method of reducing the frequency of replacing the wiping member and making the apparatus compact.
　また、布や紙類でインク組成物を払拭する方法において、布や紙類に直接メンテナンス液を付与し、濡れた状態でヘッド面を払拭することも可能である。払拭する前に塗布ユニットでメンテナンス液を付与する方法に対して、使用するメンテナンス液量が少なくてすむので、この方法も好ましく用いられる。 In the method of wiping the ink composition with a cloth or paper, it is also possible to wipe the head surface in a wet state by directly applying a maintenance liquid to the cloth or paper. This method is also preferably used because the amount of maintenance liquid to be used is smaller than the method of applying the maintenance liquid with the coating unit before wiping.
　上記ワイパブレードの材質は、弾性を有するゴムが好ましい。具体的な材質としては、ブチルゴム、クロプレンゴム、エチレンプロピレンゴム、シリコーンゴム、ウレタンゴム、ニトリルゴム等が挙げられる。ワイパブレードに撥インク性を付与するため、フッ素樹脂等によりコーティングを施したワイパブレードを用いてもよい。 The material of the wiper blade is preferably elastic rubber. Specific examples of the material include butyl rubber, chloroprene rubber, ethylene propylene rubber, silicone rubber, urethane rubber, and nitrile rubber. In order to impart ink repellency to the wiper blade, a wiper blade coated with a fluorine resin or the like may be used.
　メンテナンス液の付与量としては、インク組成物を溶解、膨潤等できる量であれば特に制限はないが、好ましくは、１～１００ｇ／ｍ２である。 The amount of maintenance liquid applied is not particularly limited as long as it can dissolve and swell the ink composition, but is preferably 1 to 100 g / m 2 .
－処理液付与工程－
　本発明における処理液付与工程は、インク組成物中の成分を凝集させる凝集成分を含有する処理液を記録媒体に付与する。記録媒体上でインク組成物と凝集成分とが混合することで、インク組成物中で安定的に分散している顔料等の凝集が促進される。 -Processing liquid application process-
In the treatment liquid application step in the present invention, a treatment liquid containing an aggregating component that aggregates the components in the ink composition is applied to the recording medium. By mixing the ink composition and the aggregating component on the recording medium, aggregation of pigments and the like stably dispersed in the ink composition is promoted.
　処理液の付与は、塗布法、インクジェット法、浸漬法等の公知の方法を適用して行なうことができる。塗布法としては、バーコーター、エクストルージョンダイコーター、エアードクターコーター、ブレードコーター、ロッドコーター、ナイフコーター、スクイズコーター、リバースロールコーター、バーコーター等を用いた公知の塗布方法によって行なうことができる。インクジェット法の詳細については、既述の通りである。 The treatment liquid can be applied by applying a known method such as a coating method, an inkjet method, or an immersion method. As a coating method, a known coating method using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater or the like can be used. The details of the inkjet method are as described above.
　凝集成分としては、画像品質の観点から、カチオンポリマー、酸性化合物、及び多価金属塩から選ばれる少なくとも１種であることが好ましい。 The aggregation component is preferably at least one selected from a cationic polymer, an acidic compound, and a polyvalent metal salt from the viewpoint of image quality.
　上記カチオンポリマーとしては、カチオン性基として、第１級～第３級アミノ基、又は第４級アンモニウム塩基を有するポリマーが好適に用いられる。カチオンポリマーは、第１級～第３級アミノ基及びその塩、又は第４級アンモニウム塩基を有する単量体（カチオン性モノマー）の単独重合体や、該カチオン性モノマーと他のモノマー（非カチオン性モノマー）との共重合体又は縮重合体として得られるものが好ましい。これらポリマーは、水溶性ポリマー又は水分散性ラテックス粒子のいずれの形態で用いてもよい。具体的には、ポリ（ビニルピリジン）塩、ポリアルキルアミノエチルアクリレート、ポリアルキルアミノエチルメタクリレート、ポリ（ビニルイミダゾール）、ポリエチレンイミン、ポリビグアニド、ポリグアニド、及びエピハロヒドリン誘導体とアミン誘導体とを含むコポリマー、及びそれらの組み合わせ等から選択される。 As the cationic polymer, a polymer having a primary to tertiary amino group or a quaternary ammonium base as a cationic group is preferably used. The cationic polymer includes a homopolymer of a monomer having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base (cationic monomer), or the cationic monomer and another monomer (non-cationic). That are obtained as a copolymer or a condensation polymer with a functional monomer). These polymers may be used in any form of water-soluble polymer or water-dispersible latex particles. Specifically, poly (vinyl pyridine) salts, polyalkylaminoethyl acrylate, polyalkylaminoethyl methacrylate, poly (vinyl imidazole), polyethyleneimine, polybiguanide, polyguanide, and copolymers comprising epihalohydrin derivatives and amine derivatives, and It is selected from combinations thereof.
　処理液は、カチオンポリマーに加え、水系溶剤（例えば、水）を用いて構成できる。
　処理液中のカチオンポリマーの含有率は、凝集効果の点で、処理液全量に対して、５～９５質量％が好ましく、１０～８０質量％がより好ましい。 The treatment liquid can be configured using an aqueous solvent (for example, water) in addition to the cationic polymer.
The content of the cationic polymer in the treatment liquid is preferably 5 to 95% by mass and more preferably 10 to 80% by mass with respect to the total amount of the treatment liquid in terms of the aggregation effect.
　上記酸性化合物としては、インク組成物のｐＨを変化させ得る化合物が挙げられる。酸性化合物としては、リン酸基、ホスホン酸基、ホスフィン酸基、硫酸基、スルホン酸基、スルフィン酸基、又はカルボキシル基を有する化合物又はその塩（例えば、多価金属塩）が挙げられる。中でも、インク組成物の凝集速度の観点から、リン酸基又はカルボキシル基を有する化合物が好ましく、カルボキシル基を有する化合物が更に好ましい。カルボキシル基を有する化合物としては、ポリアクリル酸、酢酸、グリコール酸、マロン酸、リンゴ酸、マレイン酸、アスコルビン酸、コハク酸、グルタル酸、フマル酸、クエン酸、酒石酸、乳酸、スルホン酸、オルトリン酸、ピロリドンカルボン酸、ピロンカルボン酸、ピロールカルボン酸、フランカルボン酸、ピリジンカルボン酸、クマリン酸、チオフェンカルボン酸、ニコチン酸、若しくはこれらの化合物の誘導体、又はこれらの塩（例えば、多価金属塩）等が挙げられる。 Examples of the acidic compound include compounds that can change the pH of the ink composition. Examples of the acidic compound include a compound having a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, or a carboxyl group or a salt thereof (for example, a polyvalent metal salt). Among these, from the viewpoint of the aggregation rate of the ink composition, a compound having a phosphate group or a carboxyl group is preferable, and a compound having a carboxyl group is more preferable. The compound having a carboxyl group includes polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid. , Pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, derivatives of these compounds, or salts thereof (for example, polyvalent metal salts) Etc.
　上記酸性化合物を用いる場合、処理液のｐＨ（２５℃）は、インク組成物の凝集速度の観点から、０．５～３の範囲が好ましく、０．６～２の範囲がより好ましく、０．７～１．５の範囲が更に好ましい。このとき、インク組成物のｐＨ（２５℃）は、７．５以上であることが好ましく、８以上であることがより好ましい。中でも、画像濃度、解像度、及び記録の高速化の点で、インク組成物のｐＨ（２５℃）≧７．５、かつ処理液のｐＨ（２５℃）＝０．７～１．５である場合が好ましい。 When the acidic compound is used, the pH (25 ° C.) of the treatment liquid is preferably in the range of 0.5 to 3, more preferably in the range of 0.6 to 2, from the viewpoint of the aggregation rate of the ink composition. A range of 7 to 1.5 is more preferable. At this time, the pH (25 ° C.) of the ink composition is preferably 7.5 or more, and more preferably 8 or more. In particular, the ink composition pH (25 ° C.) ≧ 7.5 and the processing solution pH (25 ° C.) = 0.7 to 1.5 in terms of image density, resolution, and high-speed recording. Is preferred.
　処理液中における酸性化合物の含有量は、凝集効果の点で、処理液全量に対して、５～９５質量％が好ましく、１０～８０質量％がより好ましい。 The content of the acidic compound in the treatment liquid is preferably 5 to 95% by mass and more preferably 10 to 80% by mass with respect to the total amount of the treatment liquid in terms of the aggregation effect.
　上記多価金属塩としては、周期表の第２属のアルカリ土類金属（例えば、マグネシウム、カルシウム）、周期表の第３属の遷移金属（例えば、ランタン）、周期表の第１３属からのカチオン（例えば、アルミニウム）、及びランタニド類（例えば、ネオジム）の塩を挙げることができる。金属の塩としては、カルボン酸塩（蟻酸、酢酸、安息香酸塩等）、硝酸塩、塩化物、及びチオシアン酸塩が好適である。中でも、好ましくは、カルボン酸（蟻酸、酢酸、安息香酸塩等）のカルシウム塩又はマグネシウム塩、硝酸のカルシウム塩又はマグネシウム塩、塩化カルシウム、塩化マグネシウム、及びチオシアン酸のカルシウム塩又はマグネシウム塩である。
　多価金属塩の処理液中における含有量は、１～１０質量％が好ましく、より好ましくは１．５～７質量％であり、更に好ましくは２～６質量％である。 Examples of the polyvalent metal salt include alkaline earth metals belonging to Group 2 of the periodic table (eg, magnesium, calcium), transition metals belonging to Group 3 of the periodic table (eg, lanthanum), and Group 13 of the periodic table. Mention may be made of salts of cations (for example aluminum) and lanthanides (for example neodymium). As the metal salt, carboxylate (formic acid, acetic acid, benzoate, etc.), nitrate, chloride, and thiocyanate are suitable. Among them, preferred are calcium salts or magnesium salts of carboxylic acids (formic acid, acetic acid, benzoates, etc.), calcium salts or magnesium salts of nitric acid, calcium chloride, magnesium chloride, and calcium salts or magnesium salts of thiocyanic acid.
The content of the polyvalent metal salt in the treatment liquid is preferably 1 to 10% by mass, more preferably 1.5 to 7% by mass, and still more preferably 2 to 6% by mass.
　処理液の粘度は、インク組成物の凝集速度の観点から、１～３０ｍＰａ・ｓが好ましく、１～２０ｍＰａ・ｓがより好ましく、２～１５ｍＰａ・ｓが更に好ましく、２～１０ｍＰａ・ｓが特に好ましい。粘度は、VISCOMETER TV-22（TOKI SANGYO CO.LTD製）を用いて２０℃で測定される値である。また、処理液の表面張力は、インク組成物の凝集速度の観点から、２０～６０ｍＮ／ｍが好ましく、２０～４５ｍＮ／ｍがより好ましく、２５～４０ｍＮ／ｍが更に好ましい。表面張力は、Automatic Surface Tensiometer CBVP-Z（協和界面科学（株）製）を用いて２５℃で測定される値である。 From the viewpoint of the aggregation rate of the ink composition, the viscosity of the treatment liquid is preferably 1 to 30 mPa · s, more preferably 1 to 20 mPa · s, further preferably 2 to 15 mPa · s, and particularly preferably 2 to 10 mPa · s. . The viscosity is a value measured at 20 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD). The surface tension of the treatment liquid is preferably 20 to 60 mN / m, more preferably 20 to 45 mN / m, and further preferably 25 to 40 mN / m from the viewpoint of the aggregation rate of the ink composition. The surface tension is a value measured at 25 ° C. using Automatic® Surface® Tensiometer® CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
　処理液付与工程は、インク組成物を用いたインク付与工程の前後のいずれに設けられてもよいが、インク付与工程前に設けられた態様が好ましい。記録媒体上に、インク組成物を付与（打滴）する前に、予めインク組成物中の成分（樹脂粒子等）を凝集させるための処理液を付与しておき、記録媒体上に付与された処理液に接触するようにインク組成物を打滴して画像化する。これにより、インクジェット記録をより高速化することができ、高速記録しても濃度、解像度の高い画像が得られる。 The treatment liquid application step may be provided before or after the ink application step using the ink composition, but an embodiment provided before the ink application step is preferable. A treatment liquid for aggregating components (resin particles, etc.) in the ink composition was applied in advance before applying (droplet ejection) the ink composition on the recording medium, and applied to the recording medium. The ink composition is ejected in contact with the treatment liquid to form an image. As a result, inkjet recording can be performed at higher speed, and an image with high density and resolution can be obtained even at high speed recording.
　また、処理液を記録媒体上に付与した後、インク組成物が付与されるまでの間に、記録媒体上の処理液を加熱乾燥することが好ましい。これにより、にじみ防止等のインク着色性が良好になり、色濃度及び色相の良好な可視画像を記録できる。 Further, it is preferable that the treatment liquid on the recording medium is heated and dried after the treatment liquid is applied onto the recording medium and before the ink composition is applied. As a result, ink coloring properties such as bleeding prevention are improved, and a visible image with good color density and hue can be recorded.
　加熱乾燥は、ヒータ等の公知の加熱手段やドライヤー等の送風を利用した送風手段、あるいはこれらを組み合わせた手段により行なえる。
　加熱方法としては、例えば、記録媒体の処理液の付与面と反対側からヒータ等で熱を与える方法や、記録媒体の処理液の付与面に温風又は熱風をあてる方法、赤外線ヒータを用いた加熱法等が挙げられ、これらの複数を組み合わせて加熱してもよい。 Heating and drying can be performed by a known heating means such as a heater, an air blowing means such as a dryer, or a combination of these.
As the heating method, for example, a method of applying heat with a heater or the like from the side opposite to the treatment liquid application surface of the recording medium, a method of applying warm air or hot air to the treatment liquid application surface of the recording medium, or an infrared heater was used. The heating method etc. are mentioned, You may heat combining these two or more.
＜メンテナンス方法＞
　本発明のメンテナンス法は、インク組成物が付着したインクジェット記録用インク吐出ヘッドに対し、既述の本発明のインクジェット記録用メンテナンス液を付与し、インクジェット記録用インク吐出ヘッド上のインク組成物を除去することを有する。メンテナンス液の構成及び好ましい態様等の詳細については、既述の通りである。 <Maintenance method>
The maintenance method of the present invention applies the above-described maintenance liquid for ink jet recording of the present invention to the ink discharge head for ink jet recording to which the ink composition is adhered, and removes the ink composition on the ink discharge head for ink jet recording. Have to do. The details of the configuration and preferred embodiment of the maintenance liquid are as described above.
　既述したように、本発明のインクジェット記録用メンテナンス液は、インク固形物の溶解性が高いので、インクジェット記録用インク吐出ヘッドにメンテナンス液を付与することで、溶解除去しやすく、その後に拭き取る等の操作によって、吐出孔の閉塞や吐出孔付近の堆積助長等の弊害を招来しにくい。 As described above, since the maintenance liquid for ink jet recording of the present invention has high solubility of ink solid matter, it can be easily dissolved and removed by applying the maintenance liquid to the ink discharge head for ink jet recording, and then wiped off, etc. By this operation, it is difficult to cause adverse effects such as blockage of the discharge holes and deposition promotion in the vicinity of the discharge holes.
　インク組成物の除去は、ヘッドのノズル面に付着するインク組成物を除去するため、ヘッド（例えば、ヘッド周辺及びインク流路等（ヘッド等））にメンテナンス液を付与する。メンテナンス液をヘッド等に付与することにより、インク組成物は溶解、膨潤等する。 The ink composition is removed by applying a maintenance liquid to the head (for example, the periphery of the head and the ink flow path (head etc.)) in order to remove the ink composition adhering to the nozzle surface of the head. By applying the maintenance liquid to the head or the like, the ink composition dissolves or swells.
　メンテナンス液の付与は、例えば、インクジェット法による吐出、ローラを用いた塗布、噴霧等により行なえる。具体的な一例として、特開２０１１－７３２９５号や特開２０１１－７３３３９号等の公報に記載の、水頭差を利用してメンテナンス液（洗浄液）塗布ユニット上にメンテナンス液柱を形成させ、そこをインクジェット記録用ヘッドが通過する際に、ヘッドとメンテナンス液塗布ユニット間に液膜が形成され、ヘッドにメンテナンス液が付与される方法でもよい。 The maintenance liquid can be applied by, for example, ejection by an inkjet method, application using a roller, spraying, or the like. As a specific example, a maintenance liquid column is formed on a maintenance liquid (cleaning liquid) application unit using a water head difference described in Japanese Patent Application Laid-Open Nos. 2011-73295, 2011-73339, and the like. When the ink jet recording head passes, a method may be used in which a liquid film is formed between the head and the maintenance liquid application unit, and the maintenance liquid is applied to the head.
　メンテナンス法は、既述の本発明の画像形成方法におけるインク除去工程と同様の操作により行なうことができる。 The maintenance method can be performed by the same operation as the ink removing step in the above-described image forming method of the present invention.
　以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” is based on mass.
　なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）で測定した。ＧＰＣは、得られたポリマーについて、溶剤を除去することによって単離し、得られた固形分をテトラヒドロフランにて０．１質量％に希釈して、ＨＬＣ－８０２０ＧＰＣ（東ソー（株）製）にて、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　Ｍｕｌｔｉｐｏｒｅ　ＨＺ－Ｈ（東ソー（株）製、４．６ｍｍＩＤ×１５ｃｍ）を３本直列につないだものをカラムとして測定した。条件は、試料濃度を０．３５質量％、流速を０．３５ｍＬ／ｍｉｎ、サンプル注入量を１０μＬ、測定温度を４０℃とし、ＲＩ検出器を用いて行なった。検量線は、東ソー（株）製「標準試料TSK standard,polystyrene」：「F-40」、「F-20」、「F-4」、「F-1」、「A-5000」、「A-2500」、「A-1000」、「ｎ－プロピルベンゼン」の８サンプルから作製した。
　また、ポリマーの酸価は、ＪＩＳ規格（ＪＩＳ Ｋ００７０：１９９２）に記載の方法により求めた。 The weight average molecular weight was measured by gel permeation chromatography (GPC). GPC was isolated by removing the solvent from the obtained polymer, and the obtained solid content was diluted to 0.1% by mass with tetrahydrofuran, and HLC-8020 GPC (manufactured by Tosoh Corporation) was used. Measurement was carried out using three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) connected in series as a column. The conditions were as follows: the sample concentration was 0.35 mass%, the flow rate was 0.35 mL / min, the sample injection amount was 10 μL, the measurement temperature was 40 ° C., and the RI detector was used. The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A -2500 "," A-1000 ", and" n-propylbenzene ".
The acid value of the polymer was determined by the method described in JIS standard (JIS K0070: 1992).
（実施例１）
＜ブラックインクＫの調製＞
－水不溶性ポリマー分散剤Ｐ－１の合成－
　以下に示すようにして水不溶性ポリマー分散剤Ｐ－１を合成した。
　攪拌機、冷却管を備えた１０００ｍｌの三口フラスコに、メチルエチルケトン８８ｇを加えて窒素雰囲気下で７２℃に加熱し、ここに、メチルエチルケトン５０ｇにジメチル２，２’－アゾビスイソブチレート０．８５ｇ、ベンジルメタクリレート６０ｇ、メタクリル酸１０ｇ、及びメチルメタクリレート３０ｇを溶解させた溶液を３時間かけて滴下した。滴下終了後、更に１時間反応させた後、メチルエチルケトン２ｇにジメチル２，２’－アゾビスイソブチレート０．４２ｇを溶解させた溶液を加え、７８℃に昇温して４時間加熱した。得られた反応溶液を大過剰量のヘキサンに２回再沈殿させ、析出した樹脂を乾燥した。このようにして、ベンジルメタクリレート／メタクリル酸／メチルメタクリレート共重合体（＝６０／１０／３０［質量比］）である水不溶性ポリマー分散剤Ｐ－１を９６ｇ得た（下記式参照）。
　得られた共重合体の組成は、１Ｈ－ＮＭＲで確認し、ＧＰＣによりポリスチレン換算で求めた重量平均分子量（Ｍｗ）は４４，６００であった。さらに、ＪＩＳ規格（ＪＩＳＫ００７０：１９９２）に記載の方法により酸価を求めたところ、６５．２ｍｇＫＯＨ／ｇであった。 Example 1
<Preparation of black ink K>
-Synthesis of water-insoluble polymer dispersant P-1-
A water-insoluble polymer dispersant P-1 was synthesized as shown below.
To a 1000 ml three-necked flask equipped with a stirrer and a condenser tube, 88 g of methyl ethyl ketone was added and heated to 72 ° C. under a nitrogen atmosphere. Here, 50 g of methyl ethyl ketone was mixed with 0.85 g of dimethyl 2,2′-azobisisobutyrate and benzyl. A solution in which 60 g of methacrylate, 10 g of methacrylic acid, and 30 g of methyl methacrylate were dissolved was dropped over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour, and then a solution of 0.42 g of dimethyl 2,2′-azobisisobutyrate dissolved in 2 g of methyl ethyl ketone was added, heated to 78 ° C. and heated for 4 hours. The obtained reaction solution was reprecipitated twice in a large excess of hexane, and the precipitated resin was dried. In this way, 96 g of a water-insoluble polymer dispersant P-1 which is a benzyl methacrylate / methacrylic acid / methyl methacrylate copolymer (= 60/10/30 [mass ratio]) was obtained (see the following formula).
The composition of the obtained copolymer was confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by polystyrene conversion by GPC was 44,600. Furthermore, when the acid value was calculated | required by the method as described in JIS specification (JISK0070: 1992), it was 65.2 mgKOH / g.
Figure JPOXMLDOC01-appb-C000013
 
Figure JPOXMLDOC01-appb-C000013
 
－顔料分散液Ｋの調製－
　カーボンブラック（ＮＩＰＥＸ１６０－ＩＱ、デグッサ社製）１０部と、上記のようにして得た水不溶性ポリマー分散剤Ｐ－１　３部と、メチルエチルケトン４２部と、１ＮのＮａＯＨ水溶液５．５部と、イオン交換水８７．２部とを混合し、ビーズミルにより０．１ｍｍφジルコニアビーズを用いて、２５００ｒｐｍで６時間分散した。得られた顔料分散液をメチルエチルケトンが充分に留去できるまで、５５℃で減圧濃縮し、更に一部の水を除去した後、高速遠心冷却機７５５０（久保田製作所社製）を用いて、８０００ｒｐｍで３０分間遠心処理（５０ｍＬ遠心菅を使用）を行ない、沈殿物を除去し、上澄み液を回収した。このようにして、樹脂被覆顔料粒子（水不溶性ポリマー分散剤で被覆された顔料）の顔料分散液Ｋを得た。
　上澄み液の吸光度スペクトルを測定し、そこから顔料濃度を求めたところ、１０．２質量％であった。また、顔料分散液Ｋ中に分散されている顔料粒子の平均粒径は、１３０ｎｍであった。 -Preparation of pigment dispersion K-
10 parts of carbon black (NIPEX 160-IQ, manufactured by Degussa), 3 parts of the water-insoluble polymer dispersant P-1 obtained as described above, 42 parts of methyl ethyl ketone, 5.5 parts of 1N NaOH aqueous solution, ions 87.2 parts of exchange water was mixed and dispersed with a bead mill using 0.1 mmφ zirconia beads at 2500 rpm for 6 hours. The obtained pigment dispersion was concentrated under reduced pressure at 55 ° C. until methyl ethyl ketone could be sufficiently distilled off, and after removing a part of the water, using a high-speed centrifugal cooler 7550 (manufactured by Kubota Seisakusho) at 8000 rpm. Centrifugation was performed for 30 minutes (using a 50 mL centrifuge), the precipitate was removed, and the supernatant was collected. Thus, a pigment dispersion K of resin-coated pigment particles (pigment coated with a water-insoluble polymer dispersant) was obtained.
When the absorbance spectrum of the supernatant was measured and the pigment concentration was determined therefrom, it was 10.2% by mass. Further, the average particle size of the pigment particles dispersed in the pigment dispersion K was 130 nm.
－自己分散性ポリマー粒子Ｂ－０１の調製－
　攪拌機、温度計、還流冷却管、及び窒素ガス導入管を備えた２リットル三口フラスコに、メチルエチルケトン５６０．０ｇを仕込んで、８７℃まで昇温した。反応容器内を、還流状態を保ちながら（以下、反応終了まで還流）、メチルメタクリレート２７８．４ｇ、イソボルニルメタクリレート２４３．６ｇ、メタクリル酸５８．０ｇ、メチルエチルケトン１０８ｇ、及び「Ｖ－６０１」（和光純薬工業（株）製）２．３２ｇからなる混合溶液を、２時間で滴下が完了するように等速で滴下した。そして、滴下完了後、１時間攪拌した。その後、「Ｖ－６０１」１．１６ｇと、メチルエチルケトン６．４ｇとからなる溶液を加え、２時間攪拌を行なった（工程（１））。続いて、工程（１）を４回繰り返し、更に「Ｖ－６０１」１．１６ｇと、メチルエチルケトン６．４ｇとからなる溶液を加えて３時間攪拌を続けた。重合反応終了後、溶液の温度を６５℃に降温し、イソプロパノール１６３．０ｇを加えて放冷した。このようにして、メチルメタクリレート／イソボルニルメタクリレート／メタクリル酸共重合体（＝４８／４２／１０［質量比］）の溶液を得た。
　得られた共重合体の重量平均分子量（Ｍｗ）は６３，０００（ＧＰＣによりポリスチレン換算で算出）、酸価は６５．１ｍｇＫＯＨ／ｇ（（ＪＩＳＫ００７０：１９９２）に記載の方法により算出）であった。 -Preparation of self-dispersing polymer particles B-01-
In a 2-liter three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 560.0 g of methyl ethyl ketone was charged and the temperature was raised to 87 ° C. While maintaining the reflux state in the reaction vessel (hereinafter refluxed until the end of the reaction), 278.4 g of methyl methacrylate, 243.6 g of isobornyl methacrylate, 58.0 g of methacrylic acid, 108 g of methyl ethyl ketone, and “V-601” (sum) A mixed solution consisting of 2.32 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was added dropwise at a constant speed so that the addition was completed in 2 hours. And after dripping completion, it stirred for 1 hour. Thereafter, a solution consisting of 1.16 g of “V-601” and 6.4 g of methyl ethyl ketone was added and stirred for 2 hours (step (1)). Subsequently, step (1) was repeated four times, and a solution consisting of 1.16 g of “V-601” and 6.4 g of methyl ethyl ketone was added and stirring was continued for 3 hours. After completion of the polymerization reaction, the temperature of the solution was lowered to 65 ° C., and 163.0 g of isopropanol was added and allowed to cool. In this way, a solution of methyl methacrylate / isobornyl methacrylate / methacrylic acid copolymer (= 48/42/10 [mass ratio]) was obtained.
The weight average molecular weight (Mw) of the obtained copolymer was 63,000 (calculated in terms of polystyrene by GPC), and the acid value was 65.1 mgKOH / g (calculated by the method described in (JISK0070: 1992)). .
　次に、得られた共重合体の溶液３１７．３ｇ（固形分濃度４１．０％）を秤量し、これにイソプロパノール４６．４ｇ、２０％無水マレイン酸水溶液１．６５ｇ（水溶性酸性化合物、共重合体に対してマレイン酸として０．３％相当）、２モル／ＬのＮａＯＨ水溶液４０．７７ｇを加え、反応容器内温度を７０℃に昇温した。次に、蒸留水３８０ｇを１０ｍｌ／ｍｉｎの速度で滴下し、水分散化した（分散工程）。
　その後、減圧下、反応容器内温度７０℃で１．５時間保って、イソプロパノール、メチルエチルケトン、蒸留水を合計で２８７．０ｇ留去した（溶剤除去工程）後、プロキセルＧＸＬ（Ｓ）（アーチ・ケミカルズ・ジャパン（株）製）０．２７８ｇ（ポリマー固形分に対してベンゾイソチアゾリン－３－オンとして４４０ｐｐｍ）を添加した。その後、１μｍのフィルターでろ過を行ない、ろ過液を回収し、固形分濃度２６．５％の自己分散性ポリマー粒子Ｂ－０１の水性分散物を得た。
　得られた自己分散性ポリマー粒子Ｂ－０１の水性分散物をイオン交換水で希釈し、２５．０％の分散液を調製し、下記の方法にて体積平均粒径を測定したところ、３．０ｎｍであった。 Next, 317.3 g (solid content concentration: 41.0%) of the obtained copolymer was weighed, and 46.4 g of isopropanol and 1.65 g of a 20% maleic anhydride aqueous solution (water-soluble acidic compound, copolymer) 40.77 g of a 2 mol / L NaOH aqueous solution was added to the polymer, and the temperature inside the reaction vessel was raised to 70 ° C. Next, 380 g of distilled water was added dropwise at a rate of 10 ml / min to disperse in water (dispersing step).
Thereafter, under reduced pressure, the temperature in the reaction vessel was kept at 70 ° C. for 1.5 hours, and 287.0 g of isopropanol, methyl ethyl ketone and distilled water were distilled off in total (solvent removal step), and then Proxel GXL (S) (Arch Chemicals) -0.278 g (manufactured by Japan Co., Ltd.) (440 ppm as benzoisothiazolin-3-one with respect to the polymer solid content) was added. Thereafter, the mixture was filtered through a 1 μm filter, and the filtrate was recovered to obtain an aqueous dispersion of self-dispersing polymer particles B-01 having a solid content concentration of 26.5%.
The obtained aqueous dispersion of self-dispersing polymer particles B-01 was diluted with ion-exchanged water to prepare a 25.0% dispersion, and the volume average particle size was measured by the following method. It was 0 nm.
（体積平均粒径（Ｍｖ）の測定）
　得られた自己分散性ポリマー粒子の水性分散物を測定に適した濃度（ローディングインデックスが０．１～１０の範囲）に適宜希釈した後、超微粒子粒度分布測定装置ナノトラックＵＰＡ－ＥＸ１５０（日機装（株）製）を用い、動的光散乱法により、各水分散物を全て同一測定条件にて体積平均粒子径を測定した。すなわち、粒子透過性：透過、粒子屈折率：１．５１、粒子形状：非球形、密度：１．２ｇ／ｃｍ３、溶剤：水、セル温度：１８～２５℃の条件において測定を行なった。 (Measurement of volume average particle diameter (Mv))
The obtained aqueous dispersion of self-dispersing polymer particles is appropriately diluted to a concentration suitable for measurement (loading index is in the range of 0.1 to 10), and then ultrafine particle size distribution analyzer Nanotrac UPA-EX150 (Nikkiso ( The volume average particle size of each aqueous dispersion was measured under the same measurement conditions by a dynamic light scattering method. That is, the measurement was performed under the conditions of particle permeability: transmission, particle refractive index: 1.51, particle shape: non-spherical, density: 1.2 g / cm 3 , solvent: water, cell temperature: 18 to 25 ° C.
～ブラックインクの調製～
　上記で得られた顔料分散液Ｋ、水不溶性ポリマー分散剤Ｐ－１、及び自己分散性ポリマー粒子Ｂ－０１を用いて、下記のインク組成になるように各成分を混合した。これをプラスチック製のディスポーザブルシリンジに詰め、ポリフッ化ビニリデン（ＰＶＤＦ）製の孔径１μｍフィルター（Ｍｉｌｌｅｘ－ＳＶ、直径２５ｍｍ、ミリポア社製）で濾過し、ブラックインク（インク組成物）Ｋ－０１を得た。 -Preparation of black ink-
Using Pigment Dispersion Liquid K obtained above, water-insoluble polymer dispersant P-1 and self-dispersing polymer particles B-01, the respective components were mixed so as to have the following ink composition. This was packed in a plastic disposable syringe and filtered through a polyvinylidene fluoride (PVDF) pore size 1 μm filter (Millex-SV, diameter 25 mm, manufactured by Millipore) to obtain a black ink (ink composition) K-01. .
（ブラックインク組成）
・ブラック顔料（カーボンブラック）・・・３．０質量％
・上記ポリマー分散剤Ｐ－１（固形分）・・・０．９質量％
・上記ポリマー粒子Ｂ－０１（固形分）・・・７．０質量％
・サンニックスＧＰ２５０・・・１０質量％
　（三洋化成工業（株）製、水溶性有機溶剤）
・トリプロピレングリコールモノメチルエーテル（ＴＰＧｍＭＥ）・・・３質量％
　（日本乳化剤（株）製ＭＦＴＧ、水溶性有機溶剤）
・ジプロピレングリコール・・・３質量％
　（和光純薬工業（株）製、水溶性有機溶剤）
・尿素・・・５質量％
　（日産化学工業（株）製、固体湿潤剤）
・オルフィンＥ１０１０・・・１．５質量％
　（日信化学工業（株）製、界面活性剤）
・セロゾール５２４　（ワックス固形分３０％、ワックス分散物）・・・２質量％
　（中京油脂（株）製、カルナウバワックス粒子（体積平均粒径７０ｎｍ））
・ニューポールＰＥ－１０８・・・０．２質量％
　（三洋化成工業（株）製、増粘剤）
・スノーテックスＸＳ・・・０．３質量％
　（日産化学（株）製、コロイダルシリカ）
・イオン交換水・・・全体で１００質量％としたときの残量
　粘度は６．５ｍＰ・ｓ（２５℃）、ｐＨは８．５（２５℃）であった。 (Black ink composition)
・ Black pigment (carbon black): 3.0% by mass
・ The above polymer dispersant P-1 (solid content) 0.9 mass%
・ Polymer particle B-01 (solid content) 7.0 mass%
・ Sanix GP250 ... 10% by mass
(Sanyo Chemical Industry Co., Ltd., water-soluble organic solvent)
・ Tripropylene glycol monomethyl ether (TPGmME) 3% by mass
(Japan Emulsifier MFTG, water-soluble organic solvent)
・ Dipropylene glycol: 3% by mass
(Water-soluble organic solvent, manufactured by Wako Pure Chemical Industries, Ltd.)
・ Urea ... 5% by mass
(Nissan Chemical Industry Co., Ltd., solid wetting agent)
・ Orphine E1010: 1.5% by mass
(Surfactant manufactured by Nissin Chemical Industry Co., Ltd.)
・ Cerosol 524 (wax solid content 30%, wax dispersion) 2 mass%
(Manufactured by Chukyo Yushi Co., Ltd., carnauba wax particles (volume average particle size 70 nm))
・ New Pole PE-108 0.2 mass%
(Thickener made by Sanyo Chemical Industries, Ltd.)
・ Snowtex XS: 0.3% by mass
(Nissan Chemical Co., Ltd., colloidal silica)
-Ion-exchanged water: Remaining amount when 100% by mass as a whole The viscosity was 6.5 mP · s (25 ° C), and the pH was 8.5 (25 ° C).
＜メンテナンス液の調製＞
　下記組成の成分を混合して、メンテナンス液を調製した。メンテナンス液は、粘度が３．１ｍＰ・ｓ（２５℃）であり、硝酸にてｐＨ８．５（２５℃）になるように調整した。粘度は、ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２（ＴＯＫＩ　ＳＡＮＧＹＯ　ＣＯ．ＬＴＤ製）により２５℃で測定した。
（メンテナンス液の組成）
・ＤＥＧｍＢＥ（一般式（II）で表される水溶性有機溶剤）・・・５．０質量％
・ＤＥＧ（保湿剤）・・・２５．０質量％
・イミダゾール（ｐＫａ＝７．０、塩基性化合物）・・・０．５質量％
・スノーテックスＸＳ・・・０．２質量％
・下記表１に示す一般式（Ｉ）で表される化合物・・・３．０質量％
・イオン交換水・・・全体で１００質量％としたときの残量
　なお、一般式（Ｉ）で表される化合物として、下記表１において「主たる化合物」として示される化合物が得られるようにアルキル基に対して付加させるエポキシの仕込み量を調整して得られたものが用いられた。 <Preparation of maintenance liquid>
A maintenance liquid was prepared by mixing components having the following composition. The maintenance liquid had a viscosity of 3.1 mP · s (25 ° C.) and was adjusted to pH 8.5 (25 ° C.) with nitric acid. The viscosity was measured at 25 ° C. by VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
(Maintenance liquid composition)
-DEGmBE (water-soluble organic solvent represented by general formula (II)): 5.0% by mass
・ DEG (humectant) ... 25.0% by mass
・ Imidazole (pKa = 7.0, basic compound) 0.5 mass%
・ Snowtex XS: 0.2% by mass
-Compound represented by general formula (I) shown in Table 1 below-3.0% by mass
・ Ion-exchanged water: the remaining amount when the total amount is 100% by mass In addition, as the compound represented by the general formula (I), an alkyl is obtained so that the compound shown as “main compound” in the following Table 1 is obtained. What was obtained by adjusting the amount of epoxy added to the group was used.
＜評価＞
　得られたメンテナンス液について、下記の評価を行なった。評価結果は、下記表１に示す。 <Evaluation>
The following evaluation was performed about the obtained maintenance liquid. The evaluation results are shown in Table 1 below.
（１）インク固形物の溶解性
　パーフルオロデシルトリクロロシラン（ＦＤＴＳ）を付与して撥水性を持たせたインクジェット記録用ヘッド表面に、強制的に上記ブラックインクをスプレーで吹き付け、室温で１時間乾燥させた。ヘッド面上の乾燥した固形物をマイクロスコープで観察、記録し、インクの直径を求めた。その後、特開２０１１－７３２９５号公報に記載の、洗浄液の液柱（洗浄液のコート層）を発生させるメンテナンス液（洗浄液）塗布ユニットを用意し、その上にメンテナンス液柱を形成した。このメンテナンス液柱に吐出ヘッドを６０ｍｍ／秒の速度で通過させ、ヘッド表面にメンテナンス液を付着させた。このヘッド表面におけるインク固形物の残り具合をマイクロスコープで観察し、洗浄前の上記直径の各インクが洗浄後に溶解して消失したかどうかに基づいてインク固形物の溶解性を評価した。
　通常はヘッドにメンテナンス液を付着させた後、布等で拭き取るが、解け残ったインクが存在すると、拭き取る際にインク吐出孔に移動し、吐出孔を閉塞したり、孔付近に堆積する等して吐出不安定化の要因になるため、拭き取らずに以下の評価基準にしたがってインク固形物の溶解性を評価した。
　<評価基準>
Ａ：直径１２μｍ以下のインク固形物を完全に溶解する。
Ｂ：直径１０μｍ以下のインク固形物を完全に溶解する。
Ｃ：直径　７μｍ以下のインク固形物を完全に溶解する。
Ｄ：直径　７μｍ以下のインク固形物が溶け残り、実用上支障を来たす可能性がある。
Ｅ：直径　５μｍ未満のインク固形物が溶け残り、実用上問題となる。 (1) Solubility of ink solid matter The above black ink is forcibly sprayed on the surface of an ink jet recording head to which perfluorodecyltrichlorosilane (FDTS) is applied to give water repellency, and dried at room temperature for 1 hour. I let you. The dried solid matter on the head surface was observed and recorded with a microscope, and the ink diameter was determined. Thereafter, a maintenance liquid (cleaning liquid) coating unit for generating a liquid column (cleaning liquid coating layer) described in JP 2011-73295 A was prepared, and a maintenance liquid column was formed thereon. The discharge head was passed through the maintenance liquid column at a speed of 60 mm / second to adhere the maintenance liquid to the head surface. The remaining state of the ink solid matter on the head surface was observed with a microscope, and the solubility of the ink solid matter was evaluated based on whether or not each ink having the above-mentioned diameter before washing dissolved and disappeared after washing.
Normally, after the maintenance liquid is attached to the head, wipe it off with a cloth, etc., but if there is undissolved ink, it will move to the ink discharge hole when wiping off, and the discharge hole will be blocked or deposited near the hole. Therefore, the ink solid solubility was evaluated according to the following evaluation criteria without wiping.
<Evaluation criteria>
A: Ink solids having a diameter of 12 μm or less are completely dissolved.
B: Ink solids having a diameter of 10 μm or less are completely dissolved.
C: Ink solids having a diameter of 7 μm or less are completely dissolved.
D: Ink solids having a diameter of 7 μm or less remain undissolved, which may impede practical use.
E: Ink solids having a diameter of less than 5 μm remain undissolved, which causes a practical problem.
（２）インク混合液の凝集性
　各メンテナンス液と上記ブラックインクとを７：３の重量比率で混合し、混合直後及び３０℃環境下に７日間放置した後のインク混合液について、体積平均粒径を測定し、その差（Δ）を下記式により求め、凝集性を評価した。Δが大きいほど経時で凝集が進んでいることを意味し、好ましくない。下記の評価基準において、Ａ～Ｃは実用上問題がなく、Ｄは吐出不良の可能性があり、Ｅは吐出不良となる可能性が高い。
　なお、体積平均粒径の測定は、上記自己分散性ポリマー粒子Ｂ－０１における測定と同様の方法にて行なった。
　体積平均粒径の差（Δ）　＝（３０℃環境下に７日間放置後の体積平均粒径）－（混合直後の体積平均粒径）
　<評価基準>
Ａ：Δ≦５ｎｍ
Ｂ：５＜Δ≦１０ｎｍ
Ｃ：１０＜Δ≦２０ｎｍ
Ｄ：２０＜Δ≦５０ｎｍ
Ｅ：５０＜Δ (2) Cohesiveness of ink mixed liquid Each maintenance liquid and the above black ink are mixed at a weight ratio of 7: 3, and the volume average particle size of the ink mixed liquid immediately after mixing and after standing in a 30 ° C. environment for 7 days. The diameter was measured, the difference (Δ) was determined by the following formula, and the cohesiveness was evaluated. Larger Δ means that aggregation is progressing with time, which is not preferable. In the following evaluation criteria, A to C have no practical problem, D has a possibility of ejection failure, and E has a high possibility of ejection failure.
The volume average particle diameter was measured by the same method as that for the self-dispersing polymer particle B-01.
Volume average particle size difference (Δ) = (Volume average particle size after standing for 7 days in 30 ° C. environment) − (Volume average particle size immediately after mixing)
<Evaluation criteria>
A: Δ ≦ 5 nm
B: 5 <Δ ≦ 10 nm
C: 10 <Δ ≦ 20 nm
D: 20 <Δ ≦ 50 nm
E: 50 <Δ
（３）インク混合液の乾燥後の水溶解性
　各メンテナンス液と上記ブラックインクを７：３の重量比率で混合し、その混合液をヘッド表面と同じ撥水膜をコートしたテストピース上に１０μｌ滴下し、２５℃８０％の環境下で２４ｈｒ放置後、３０ｍｌの水の中に浸漬し、乾燥後の混合液について水への溶解性を評価した。不溶解物が発生すると、吐出口で析出、付着する可能性があり、経時で吐出性を悪化させる。
　<評価基準>
Ａ：完全に水に溶解する。
Ｂ：極僅かに水不溶解物が発生。
Ｃ：いくらか水不溶解物が見られるが実用上問題ないレベル。
Ｄ：水不溶解物が見られ、乾燥時に不吐出の原因になる可能性がある。
Ｅ：水不溶解物が多く、実用上問題になる可能性が高い。 (3) Water solubility after drying of ink mixture Each maintenance solution and the black ink are mixed at a weight ratio of 7: 3, and the mixed solution is 10 μl on a test piece coated with the same water-repellent film as the head surface. The solution was added dropwise and allowed to stand for 24 hours in an environment of 25 ° C. and 80%, and then immersed in 30 ml of water, and the dried mixture was evaluated for solubility in water. If an insoluble material is generated, it may be deposited and deposited at the discharge port, and the discharge property deteriorates over time.
<Evaluation criteria>
A: Completely soluble in water.
B: Slightly water-insoluble matter is generated.
C: A level in which some water insolubles are observed but there is no practical problem.
D: Water-insoluble matter is observed, which may cause non-ejection during drying.
E: There are many water-insoluble substances, and there is a high possibility of causing a problem in practical use.
Figure JPOXMLDOC01-appb-T000014
 
　実験番号１４では、ＰＥＧ（６）モノデシルエーテルとＰＥＧ（７）モノデシルエーテルの１：１混合物を用いた。
Figure JPOXMLDOC01-appb-T000014

In Experiment No. 14, a 1: 1 mixture of PEG (6) monodecyl ether and PEG (7) monodecyl ether was used.
　上記表１に示すように、ＨＬＢ値が１０．５～１３．８の一般式（Ｉ）で表される化合物及び一般式（ＩＩ）で表される水溶性有機溶剤を含有する本発明の組成では、インク固形物の溶解性に優れ、インク混合液の凝集性、インク混合液の乾燥時の水溶解性に優れるメンテナンス液が得られた。　
　ＨＬＢ値が１０．５～１３．８の一般式（Ｉ）で表される化合物の中でも、Ｒ１がオクチル基又はデシル基の化合物がより好ましく、特にＲ１がデシル基の化合物で、より好ましい結果が得られた。
　また、ＨＬＢ値が１０．５～１３．８の一般式（Ｉ）で表される化合物の中でも、Ｒ１の炭素数が小さいとインク固形物の溶解性が低下し、逆にＲ１の炭素数が大きいとインク混合液の凝集性及びインク混合液の乾燥時の水溶解性に低下する傾向が見られた。 As shown in Table 1 above, the composition of the present invention containing a compound represented by the general formula (I) having an HLB value of 10.5 to 13.8 and a water-soluble organic solvent represented by the general formula (II) Thus, a maintenance liquid having excellent solubility of ink solid matter, cohesion of the ink mixture, and water solubility when drying the ink mixture was obtained.
Among the compounds represented by the general formula (I) having an HLB value of 10.5 to 13.8, a compound in which R 1 is an octyl group or a decyl group is more preferable, and in particular, a compound in which R 1 is a decyl group is more preferable. Results were obtained.
Further, among the compounds represented by the general formula (I) having an HLB value of 10.5 to 13.8, if the carbon number of R 1 is small, the solubility of the ink solid matter decreases, and conversely the carbon of R 1 When the number was large, there was a tendency that the cohesiveness of the ink mixture and the water solubility during drying of the ink mixture were lowered.
（実施例２）
＜メンテナンス液の調製＞
　実施例１の「Ｎｏ．１３」のメンテナンス液の調製において、組成中の溶剤であるＤＥＧｍＢＥ及び保湿剤であるＤＥＧを、それぞれ下記表２に示す等質量の化合物に変更したこと以外は、Ｎｏ．１３と同様にして、メンテナンス液を調液し、実施例１と同様にして評価した。 (Example 2)
<Preparation of maintenance liquid>
In the preparation of the maintenance liquid of “No. 13” in Example 1, the solvent in the composition, DEGmBE and the moisturizer DEG, were changed to compounds of the same mass shown in Table 2 below, respectively. The maintenance liquid was prepared in the same manner as in Example 13 and evaluated in the same manner as in Example 1.
Figure JPOXMLDOC01-appb-T000015
 
Figure JPOXMLDOC01-appb-T000015
 
　上記表２中に記載の各溶剤種の詳細は、以下の通りである。
ＤＥＧｍＢＥ　…　ジエチレングリコールモノブチルエーテル
ＴＥＧｍＢＥ　…　トリエチレングリコールモノブチルエーテル
ＤＥＧｍＥＥ　…　ジエチレングリコールモノエチルエーテル
ＤＰＧｍＭＥ　…　ジプロピレングリコールモノメチルエーテル
ＤＥＧ　　　　…　ジエチレングリコール
ＤＰＧ　　　　…　ジプロピレングリコール
ＰＧ　　　　　…　プロピレングリコール
ＴＥＧ　　　　…　トリエチレングリコール Details of the solvent types described in Table 2 are as follows.
DEGmBE ... Diethylene glycol monobutyl ether TEGmBE ... Triethylene glycol monobutyl ether DEGmEE ... Diethylene glycol monoethyl ether DPGmME ... Dipropylene glycol monomethyl ether DEG ... Diethylene glycol DPG ... Dipropylene glycol PG ... Propylene glycol TEG ... Triethylene glycol
（実施例３）
＜メンテナンス液の調製＞
　実施例１の「Ｎｏ．１３」のメンテナンス液の調製において、組成中の溶剤であるＤＥＧｍＢＥ及び保湿剤であるＤＥＧを、それぞれ下記表３に示すように添加量を変更したこと以外は、Ｎｏ．１３と同様にして、メンテナンス液を調液し、実施例１と同様にして評価した。 (Example 3)
<Preparation of maintenance liquid>
In the preparation of the maintenance liquid of “No. 13” in Example 1, the amount of addition of DEGmBE, which is a solvent in the composition, and DEG, which is a humectant, was changed as shown in Table 3 below. The maintenance liquid was prepared in the same manner as in Example 13 and evaluated in the same manner as in Example 1.
Figure JPOXMLDOC01-appb-T000016
 
Figure JPOXMLDOC01-appb-T000016
 
　表３に示すように、ＤＥＧｍＢＥとＤＥＧとの質量比（ＤＥＧｍＢＥ：ＤＥＧ）が、１：２～１：９、更には１：３～１：５である本発明の組成では、インク固形物の溶解性に優れ、インク混合液の凝集性、インク混合液の乾燥時の水溶解性に優れるメンテナンス液が得られた。 As shown in Table 3, in the composition of the present invention in which the mass ratio of DEGmBE to DEG (DEGmBE: DEG) is 1: 2 to 1: 9, further 1: 3 to 1: 5, A maintenance liquid excellent in solubility, cohesiveness of the ink mixture, and water solubility during drying of the ink mixture was obtained.
（実施例４）
＜着色インクの調製＞
　特開２０１１－４６９０８号公報の段落番号［０２２１］及び表２～３に記載の、マゼンタインク（Ｍ－２１）、シアンインク（Ｃ－２１）、イエローインク（Ｙ－２１）、及びブラックインク（Ｋ－２１）の調製をした。 (Example 4)
<Preparation of colored ink>
Magenta ink (M-21), cyan ink (C-21), yellow ink (Y-21), and black ink (described in paragraph number [0221] and Tables 2 to 3 of JP2011-46908A) K-21) was prepared.
＜処理液の調製＞
　下記組成の成分を混合して、処理液を調製した。処理液の物性は、粘度２．６ｍＰａ・ｓ、表面張力４１．０ｍＮ／ｍ、ｐＨ（２５℃）０．７であった。なお、粘度は、ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２（ＴＯＫＩ　ＳＡＮＧＹＯ　ＣＯ．ＬＴＤ製）を用いて２０℃の条件下で測定した。表面張力は、Ａｕｔｏｍａｔｉｃ　Ｓｕｒｆａｃｅ　Ｔｅｎｓｉｏｍｅｔｅｒ　ＣＢＶＰ－Ｚ（協和界面科学（株）製）を用いて２５℃の条件下で測定した。 <Preparation of treatment solution>
The processing liquid was prepared by mixing components having the following composition. The physical properties of the treatment liquid were a viscosity of 2.6 mPa · s, a surface tension of 41.0 mN / m, and a pH (25 ° C.) of 0.7. The viscosity was measured under the condition of 20 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD). The surface tension was measured at 25 ° C. using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
（処理液の組成）
・ＴＰＧｍＭＥ・・・４．８質量％
・ＤＥＧｍＢＥ（ジエチレングリコールモノブチルエーテル）・・・４．８質量％
・マロン酸・・・９．０質量％
・リンゴ酸・・・７．８質量％
・燐酸８５質量％水溶液・・・６．７質量％
・1,2,3-プロパントリカルボン酸・・・２．５質量％
・下記水溶性ポリマー１・・・０．６質量％
・ベンゾトリアゾール・・・１．５質量％
・ＴＳＡ－７３９（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製消泡剤）・・・シリコーンオイルの量として１００ｐｐｍ
・イオン交換水・・・全体で１００質量％としたときの残量 (Composition of treatment liquid)
・ TPGmME ・ ・ ・ 4.8% by mass
・ DEGmBE (diethylene glycol monobutyl ether): 4.8% by mass
・ Malonic acid: 9.0% by mass
-Malic acid: 7.8% by mass
・ 85% by mass aqueous solution of phosphoric acid ... 6.7% by mass
・ 1,2,3-propanetricarboxylic acid: 2.5% by mass
・ The following water-soluble polymer 1 ... 0.6% by mass
・ Benzotriazole: 1.5% by mass
・ TSA-739 (Momentive Performance Materials Japan Defoamer) ・ 100ppm as the amount of silicone oil
・ Ion-exchanged water: Remaining amount when 100% by mass as a whole
Figure JPOXMLDOC01-appb-C000017
 
Figure JPOXMLDOC01-appb-C000017
 
＜メンテナンス液の調製＞
　下記組成の成分を混合して、メンテナンス液を調製した。メンテナンス液は、粘度が３．１（２５℃）であり、硝酸にてｐＨ８．４になるように調整した。粘度の測定は実施例１と同様にして行なった。
（メンテナンス液の組成）
・ＤＥＧｍＢＥ（一般式（II）で表される水溶性有機溶剤）・・・７．０質量％
・ＤＥＧ（保湿剤）・・・２３．０質量％
・イミダゾール（ｐＫａ＝７．０、塩基性化合物）・・・０．５質量％
・ベンゾトリアゾール・・・０．１質量％
・スノーテックスＸＳ・・・０．１質量％
　（日産化学（株）製、コロイダルシリカ）
・下記表４に示す一般式（Ｉ）で表される化合物・・・３．０質量％
・イオン交換水・・・全体で１００質量％としたときの残量 <Preparation of maintenance liquid>
A maintenance liquid was prepared by mixing components having the following composition. The maintenance liquid had a viscosity of 3.1 (25 ° C.) and was adjusted to pH 8.4 with nitric acid. The viscosity was measured in the same manner as in Example 1.
(Maintenance liquid composition)
-DEGmBE (water-soluble organic solvent represented by formula (II)) ... 7.0% by mass
・ DEG (humectant) ... 23.0% by mass
・ Imidazole (pKa = 7.0, basic compound) 0.5 mass%
・ Benzotriazole 0.1% by mass
・ Snowtex XS ... 0.1% by mass
(Nissan Chemical Co., Ltd., colloidal silica)
-Compound represented by general formula (I) shown in Table 4 below: 3.0% by mass
・ Ion-exchanged water: Remaining amount when 100% by mass as a whole
＜画像形成及び評価＞
Ａ．画像形成
　図１に示すインクジェット記録装置を用意し、４色の上記着色インクを以下のように吐出することによりインク画像を形成した。記録媒体としては、坪量１０４～１５４ｇ／ｍ２のＯＫトップコート＋（王子製紙（株）製）を用いた。また、画像形成条件は、解像度：１２００ｄｐｉ（dot per inch）×１２００ｄｐｉ、吐出液滴量：３ｐＬ相当とした。 <Image formation and evaluation>
A. Image formation The ink jet recording apparatus shown in FIG. 1 was prepared, and ink images were formed by ejecting the four colored inks as follows. As a recording medium, an OK top coat with a basis weight of 104 to 154 g / m 2 + (manufactured by Oji Paper Co., Ltd.) was used. The image forming conditions were resolution: 1200 dpi (dot per inch) × 1200 dpi, and ejection droplet amount: equivalent to 3 pL.
　図１に示すインクジェット記録装置１に、あらかじめ調製しておいた４色の着色インク、処理液、及びメンテナンス液を装填した。
　なお、図１において、１は、インクジェット記録装置であり、１０は給紙部であり、１２は処理液付与部であり、１４は描画部であり、１６は乾燥部であり、１８は定着部であり、２０は排出部であり、２２は記録媒体であり、２４は第１の中間搬送部であり、２６は第２の中間搬送部であり、２８は第３の中間搬送部であり、３０は中間搬送体であり、３２は搬送ガイドであり、５０はフィーダーボードであり、５２は給紙胴であり、７０は描画ドラムであり、７２Ｃ，７２Ｍ，７２Ｙ，７２Ｋはそれぞれインクヘッドであり、７６は乾燥ドラムであり、８４は定着ドラムであり、８６は第１定着ローラであり、８８は第２定着ローラであり、９０はインラインセンサーであり、９２は排紙台であり、９４はチェーンデリバリーのスプロケットであり、９６はチェーンデリバリーのチェーンであり、９８は装置の外カバーである。
　インクジェット記録装置を起動し、給紙部１０から繰り出された記録媒体２２に対して、処理液ドラム５４（直径４５０ｍｍ）上で、処理液塗布装置５６によって処理液を全面に薄膜塗布（２μｍ厚）した。このとき、処理液塗布装置５６としてグラビアローラを使用した。
　次いで、処理液を塗布した記録媒体２２を温風噴出しノズル５８（７０℃温風（９ｍ３／分）の吹き付け）とＩＲヒータ６０（１８０℃）によって乾燥処理し、処理液中の溶剤の一部を乾燥させた。
　この記録媒体２２を第１の中間搬送部２４を介して描画部１４に搬送し、各色ベタ画像用の画像信号に応じて、ＣＭＹ（シアン・マゼンダ・イエロー）のそれぞれの着色インクを吐出ヘッド７２Ｙ、７２Ｍ、７２Ｃからそれぞれ吐出し、記録媒体上に画像様に打滴した。インク吐出体積は、ハイライト部では１．４ｐｌ、高濃度部では３ｐｌ（２ｄｒｏｐｓ）とし、記録密度は主走査・副走査方向共に１２００ｄｐｉで記録されるようにした。その際、不吐出ノズルが発生した場合は、不吐出ノズルの隣接ノズルから５ｐｌ（３ｄｒｏｐｓ）を吐出できるようにし、不吐出によるスジムラを見え難くする処理を行なった。また、処理液ドラム５４、乾燥ドラム７６を描画ドラム７０と別に設けたことにより、処理液の乾燥を高速で行なう場合にも、その熱や風の悪影響が描画部に及ぶ事が無く、安定吐出が達成された。
　次いで、乾燥ドラム７６上では、第１のＩＲヒータ７８（表面温度１８０℃）、温風噴出しノズル８０（７０℃温風（１２ｍ３／分）の風量）、及び第２のＩＲヒータ８２（表面温度１８０℃）により乾燥させた。乾燥時間は、約２秒である。
　次に、画像が形成された記録媒体２２を、５０℃の定着ドラム８４と、８０℃の第１定着ローラ８６及び第２定着ローラ８８とによって、０．３０ＭＰａのニップ圧で加熱定着した。このとき、第１定着ローラ８６、第２定着ローラ８８としては、金属製の心金に硬度３０°のシリコーンゴムを６ｍｍの厚さで設け、その上にソフトＰＦＡ被覆（５０μｍ
厚）を施し、インク画像に対する密着性及び剥離性に優れたものを使用した。
　記録媒体２２は、各ドラム５４、７０、７６、８４によるドラム搬送によって５３５ｍｍ／ｓの搬送速度で搬送されるようにした。
　以上の工程を経て、画像形成された記録媒体の評価サンプルを得た。 The ink jet recording apparatus 1 shown in FIG. 1 was loaded with four colored inks prepared in advance, a treatment liquid, and a maintenance liquid.
In FIG. 1, 1 is an ink jet recording apparatus, 10 is a paper feeding unit, 12 is a treatment liquid application unit, 14 is a drawing unit, 16 is a drying unit, and 18 is a fixing unit. 20 is a discharge unit, 22 is a recording medium, 24 is a first intermediate conveyance unit, 26 is a second intermediate conveyance unit, and 28 is a third intermediate conveyance unit, 30 is an intermediate conveyance body, 32 is a conveyance guide, 50 is a feeder board, 52 is a paper feed cylinder, 70 is a drawing drum, and 72C, 72M, 72Y, and 72K are ink heads, respectively. , 76 is a drying drum, 84 is a fixing drum, 86 is a first fixing roller, 88 is a second fixing roller, 90 is an inline sensor, 92 is a paper discharge table, and 94 is Chain delivery sprocket A DOO, 96 is the chain of the chain delivery 98 is the outer cover of the device.
The ink jet recording apparatus is activated, and the processing liquid is applied to the entire surface by the processing liquid coating device 56 on the processing liquid drum 54 (diameter 450 mm) on the recording medium 22 fed from the paper supply unit 10 (2 μm thickness). did. At this time, a gravure roller was used as the treatment liquid coating device 56.
Next, the recording medium 22 coated with the treatment liquid is dried by a warm air jet nozzle 58 (70 ° C. warm air (9 m 3 / min) sprayed) and an IR heater 60 (180 ° C.) to remove the solvent in the treatment liquid. Part was dried.
The recording medium 22 is transported to the drawing unit 14 via the first intermediate transport unit 24, and CMY (cyan, magenta, yellow) colored inks are ejected from the ejection head 72Y according to the image signal for each color solid image. , 72M, and 72C, and ejected onto the recording medium like an image. The ink discharge volume was 1.4 pl in the highlight area and 3 pl (2 drops) in the high density area, and the recording density was recorded at 1200 dpi in both the main scanning and sub-scanning directions. At that time, when a non-ejection nozzle occurs, 5 pl (3 drops) can be ejected from a nozzle adjacent to the non-ejection nozzle, and a process of making it difficult to see non-ejection stripes is performed. Further, since the processing liquid drum 54 and the drying drum 76 are provided separately from the drawing drum 70, even when the processing liquid is dried at a high speed, the adverse effect of the heat and wind does not reach the drawing section, and stable discharge is achieved. Was achieved.
Next, on the drying drum 76, a first IR heater 78 (surface temperature 180 ° C.), a warm air ejection nozzle 80 (air flow of 70 ° C. warm air (12 m 3 / min)), and a second IR heater 82 ( The surface temperature was 180 ° C.). The drying time is about 2 seconds.
Next, the recording medium 22 on which the image was formed was heat-fixed with a nip pressure of 0.30 MPa by a fixing drum 84 at 50 ° C., a first fixing roller 86 and a second fixing roller 88 at 80 ° C. At this time, as the first fixing roller 86 and the second fixing roller 88, a silicone rubber having a hardness of 30 ° is provided on a metal mandrel with a thickness of 6 mm, and a soft PFA coating (50 μm) is provided thereon.
Thickness) was used, and a material excellent in adhesion and peelability to ink images was used.
The recording medium 22 was conveyed at a conveyance speed of 535 mm / s by drum conveyance by the drums 54, 70, 76, and 84.
Through the above steps, an evaluation sample of a recording medium on which an image was formed was obtained.
　次に、インクの吐出を完了した後、インクジェット記録装置に装填された下記のメンテナンス液をヘッドのノズル面にメンテナンス液塗布ユニットから付与した後、トレシーを用いて吐出ヘッドの複数の吐出孔が配列されたノズル面をワイピングした。 Next, after the ink discharge is completed, the following maintenance liquid loaded in the inkjet recording apparatus is applied to the nozzle surface of the head from the maintenance liquid application unit, and then a plurality of discharge holes of the discharge head are arranged using the tresy The nozzle surface was wiped.
Ｂ．評価２
　得られたメンテナンス液を用い、下記のメンテナンス性の評価を行なった。評価結果を下記表４に示す。 B. Evaluation 2
The following maintenance property was evaluated using the obtained maintenance liquid. The evaluation results are shown in Table 4 below.
＜メンテナンス性＞
　上記のように画像形成するに際して、吐出等を下記（ア）～（ウ）の条件で行ない、その後の再吐出性を評価し、メンテナンス性の合否を判定した。合否判定の結果から、下記評価基準にしたがってメンテナンス性を評価した。
～吐出等の条件と合否の判定基準～
（ア）インクを４５分連続吐出し、吐出終了直後にメンテナンス液を吐出ヘッドのノズル面に付与してワイピングを１回実施し、その後のインク吐出率が９０％以上の場合、合格とした。
（イ）インクを５分連続吐出し、吐出後３０分休止し、休止後にメンテナンス液を吐出ヘッドのノズル面に付与してワイピングを１回実施し、その後のインク吐出率が９０％以上の場合、合格とした。
（ウ）インクの５分連続吐出し、吐出終了直後にメンテナンス液をヘッドのノズル面に付与してワイピングを１回実施し、その後４５分放置後、インク吐出率が９０％以上の場合、合格とした。
　～インク吐出率の測定～
　インク吐出開始時に全ノズルからインクを吐出していることを確認し、ワイピング後の吐出ノズル数をカウントして、下記式から吐出率を算出した。
　　吐出率（％）＝（ワイピング後の吐出ノズル数）／（全ノズル数）×１００
　<評価基準>
Ａ：上記ア～ウの３項目とも合格
Ｂ：上記ア～ウの２項目が合格
Ｃ：上記ア～ウの１項目のみが合格
Ｄ：上記ア～ウの３項目とも不合格 <Maintenance>
When an image was formed as described above, ejection or the like was performed under the following conditions (a) to (c), and the subsequent re-ejectability was evaluated to determine whether the maintenance performance was acceptable. From the result of the pass / fail judgment, the maintainability was evaluated according to the following evaluation criteria.
~ Discharge conditions and acceptance criteria ~
(A) Ink was continuously ejected for 45 minutes, and immediately after the ejection was completed, the maintenance liquid was applied to the nozzle surface of the ejection head, and wiping was performed once. If the ink ejection rate thereafter was 90% or more, the test was accepted.
(A) When ink is ejected continuously for 5 minutes, paused for 30 minutes after ejection, maintenance liquid is applied to the nozzle surface of the ejection head after the rest and wiping is performed once, and the subsequent ink ejection rate is 90% or more And passed.
(C) Ink is ejected continuously for 5 minutes. Immediately after the ejection is completed, the maintenance liquid is applied to the nozzle surface of the head and wiping is performed once. Then, after 45 minutes, the ink ejection rate is 90% or more. It was.
-Measurement of ink ejection rate-
It was confirmed that ink was ejected from all nozzles at the start of ink ejection, the number of ejection nozzles after wiping was counted, and the ejection rate was calculated from the following equation.
Discharge rate (%) = (number of discharge nozzles after wiping) / (total number of nozzles) × 100
<Evaluation criteria>
A: All three items A to U pass B: Two items A to U pass C: Only one item A to U passes D: All three items A to U fail
Figure JPOXMLDOC01-appb-T000018
 
Figure JPOXMLDOC01-appb-T000018
 
（実施例５）
　実施例４の「Ｎｏ．４８」のメンテナンス液の調製において、Ｎｏ．４８組成中のイミダゾールを取り除いたこと以外は、Ｎｏ．４８と同様にしてメンテナンス液を調製した。 (Example 5)
In the preparation of the maintenance liquid “No. 48” in Example 4, No. 48 except that imidazole in the composition was removed. A maintenance liquid was prepared in the same manner as in No.48.
　このメンテナンス液では、６０℃で７日間経時させた後、ｐＨ低下が生じた。このメンテナンス液を用い、実施例４と同様の方法でメンテナンス性を評価したところ、悪化することが分かった。
　このｐＨ低下は、上記一般式（Ｉ）で表される化合物（界面活性剤）を添加すると大きくなっており、イミダゾール添加によりメンテナンス性の悪化を防いでいることが確認された。 With this maintenance liquid, pH reduction occurred after aging at 60 ° C. for 7 days. When this maintenance liquid was used and the maintenance performance was evaluated in the same manner as in Example 4, it was found that the maintenance liquid deteriorated.
This decrease in pH was increased when the compound (surfactant) represented by the above general formula (I) was added, and it was confirmed that the addition of imidazole prevented the deterioration of the maintainability.
（実施例６）
　実施例４の「Ｎｏ．４８」のメンテナンス液の調製において、消泡剤として、ＢＹＫ－０１２、０１７、０２１、０２２、０２４、０２５、０３８、０９４（ビックケミー・ジャパン（株）製）、ＫＳ－５３７、ＫＳ－６０４、ＫＭ－７２Ｆ（信越化学工業（株）製）、ＴＳＡ－７３９（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）、オルフィンＡＦ１０４（日信化学工業（株）製）をそれぞれ０．０１質量％添加して、メンテナンス性、及びメンテナンス後のスジ発生頻度について評価した。 (Example 6)
In the preparation of the maintenance liquid of “No. 48” in Example 4, as the antifoaming agent, BYK-012, 017, 021, 022, 024, 025, 038, 094 (manufactured by BYK Japan Japan Co., Ltd.), KS- 537, KS-604, KM-72F (manufactured by Shin-Etsu Chemical Co., Ltd.), TSA-739 (manufactured by Momentive Performance Materials Japan GK), Olfin AF104 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.01% by mass was added to evaluate the maintainability and the frequency of streaks after maintenance.
　その結果、これら消泡剤の添加によれば、メンテナンス性、メンテナンス後のスジ発生に対して良好な効果が得られることを確認した。本発明の一般式（Ｉ）で表わされる化合物は、泡立ちし易くなる傾向があるが、特に水系のシリコーン消泡剤であるＢＹＫ－０２４の添加によれば、メンテナンス性、メンテナンス後のスジ発生ともに、最も好ましい効果が得られることを確認した。 As a result, according to the addition of these antifoaming agents, it was confirmed that good effects can be obtained with respect to maintenance performance and generation of streaks after maintenance. Although the compound represented by the general formula (I) of the present invention tends to be easily foamed, especially by adding BYK-024, which is a water-based silicone antifoaming agent, both maintainability and generation of streaks after maintenance are achieved. It was confirmed that the most preferable effect was obtained.
　日本出願第２０１２－１２２５３７の開示はその全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The entire disclosure of Japanese Application No. 2012-122537 is incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims (10)

  1. 　ＨＬＢ値が１０．５～１３．８の下記一般式（Ｉ）で表される化合物と、下記一般式（ＩＩ）で表される水溶性有機溶剤と、保湿剤と、水とを含有するインクジェット記録用メンテナンス液。
    Figure JPOXMLDOC01-appb-C000001
     
    〔一般式（ＩＩ）中、Ｒ１は、炭素数６～２０の直鎖もしくは分岐のアルキル基、炭素数６～２０の直鎖もしくは分岐のアルケニル基、又はアリール基を表す。ｍは、３～１４の整数を表す。〕
    Figure JPOXMLDOC01-appb-C000002
     
    〔一般式（Ｉ）中、Ｒ３及びＲ５は、各々独立に水素原子又は炭素数１～４のアルキル基を表し、Ｒ４はエチレン基又はプロピレン基を表す。但し、Ｒ３とＲ５が同時に水素原子であることはない。ｘは、１～４の整数を表す。〕     An inkjet containing a compound represented by the following general formula (I) having an HLB value of 10.5 to 13.8, a water-soluble organic solvent represented by the following general formula (II), a humectant, and water Maintenance fluid for recording.
    Figure JPOXMLDOC01-appb-C000001

    [In general formula (II), R 1 represents a linear or branched alkyl group having 6 to 20 carbon atoms, a linear or branched alkenyl group having 6 to 20 carbon atoms, or an aryl group. m represents an integer of 3 to 14. ]
    Figure JPOXMLDOC01-appb-C000002

    [In general formula (I), R 3 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 represents an ethylene group or a propylene group. However, R 3 and R 5 are not hydrogen atoms at the same time. x represents an integer of 1 to 4. ]
  2. 　一般式（Ｉ）において、Ｒ１が、炭素数８～１０の直鎖もしくは分岐のアルキル基である請求項１に記載のインクジェット記録用メンテナンス液。 2. The maintenance liquid for inkjet recording according to claim 1, wherein R 1 in the general formula (I) is a linear or branched alkyl group having 8 to 10 carbon atoms.
  3. 　前記水溶性有機溶剤及び前記保湿剤の合計の含有量が、インクジェット記録用メンテナンス液の全量に対して２０～４０質量％であり、前記水溶性有機溶剤と前記保湿剤との質量比〔水溶性有機溶剤：保湿剤〕が１：１～１：１００である請求項１又は請求項２に記載のインクジェット記録用メンテナンス液。 The total content of the water-soluble organic solvent and the humectant is 20 to 40% by mass with respect to the total amount of the maintenance liquid for inkjet recording, and the mass ratio of the water-soluble organic solvent and the humectant [water-soluble The maintenance liquid for inkjet recording according to claim 1 or 2, wherein the organic solvent: humectant] is 1: 1 to 1: 100.
  4. 　更に、ｐＫａ値６．０～８．５の塩基性化合物を含有する請求項１～請求項３のいずれか１項に記載のインクジェット記録用メンテナンス液。 The maintenance liquid for inkjet recording according to any one of claims 1 to 3, further comprising a basic compound having a pKa value of 6.0 to 8.5.
  5. 　更に、シリコーン系消泡剤を含有する請求項１～請求項４のいずれか１項に記載のインクジェット記録用メンテナンス液。 The maintenance liquid for inkjet recording according to any one of claims 1 to 4, further comprising a silicone-based antifoaming agent.
  6. 　顔料とポリマー粒子と水とを含有するインク組成物と、
    　請求項１～請求項５のいずれか１項に記載のインクジェット記録用メンテナンス液と、を有するインクジェット記録用インクセット。     An ink composition containing a pigment, polymer particles, and water;
    An ink set for ink jet recording comprising the maintenance liquid for ink jet recording according to any one of claims 1 to 5.
  7. 　更に、前記インク組成物中の成分を凝集させる凝集成分を含有する処理液を有する請求項６に記載のインクジェット記録用インクセット。 The ink set for inkjet recording according to claim 6, further comprising a treatment liquid containing an aggregating component that agglomerates the components in the ink composition.
  8. 　請求項６又は請求項７に記載のインクジェット記録用インクセットが用いられ、
    　インク組成物をインクジェット記録用ヘッドから吐出することで、インク組成物を記録媒体に付与するインク付与工程と、
    　前記インクジェット記録用ヘッドに付着したインク組成物をインクジェット記録用メンテナンス液により除去するインク除去工程と、を有する画像形成方法。     The ink set for inkjet recording according to claim 6 or 7, is used,
    An ink application step of applying the ink composition to a recording medium by discharging the ink composition from an inkjet recording head; and
    An ink removing step of removing the ink composition adhering to the ink jet recording head with a maintenance liquid for ink jet recording.
  9. 　更に、前記インク組成物中の成分を凝集させる凝集成分を含有する処理液を記録媒体に付与する処理液付与工程を有する請求項８に記載の画像形成方法。 The image forming method according to claim 8, further comprising a treatment liquid application step of applying a treatment liquid containing an aggregating component for aggregating the components in the ink composition to a recording medium.
  10. 　インク組成物が付着したインクジェット記録用インク吐出ヘッドに対し、請求項１～請求項５のいずれか１項に記載のインクジェット記録用メンテナンス液を付与し、前記インクジェット記録用ヘッド上のインク組成物を除去することを含むメンテナンス方法。 6. The inkjet recording maintenance liquid according to any one of claims 1 to 5 is applied to an inkjet recording ink discharge head to which the ink composition is adhered, and the ink composition on the inkjet recording head is used as an ink composition. Maintenance method including removing.
PCT/JP2013/064670 2012-05-29 2013-05-27 Maintenance fluid for inkjet recording, ink set for inkjet recording, image forming method, and maintenance method WO2013180074A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2014518435A JP5823613B2 (en) 2012-05-29 2013-05-27 Inkjet recording maintenance liquid, inkjet recording ink set, image forming method, and maintenance method
EP13796414.4A EP2857204B1 (en) 2012-05-29 2013-05-27 Maintenance liquid for inkjet recording, ink set for inkjet recording, image forming method, and maintenance method
CN201380027866.5A CN104349901B (en) 2012-05-29 2013-05-27 Ink mist recording Precerving liquid, ink for ink-jet recording group, image forming method and maintenance method
US14/552,502 US9133359B2 (en) 2012-05-29 2014-11-25 Maintenance liquid for inkjet recording, ink set for inkjet recording, image forming method, and maintenance method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-122537 2012-05-29
JP2012122537 2012-05-29

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/552,502 Continuation US9133359B2 (en) 2012-05-29 2014-11-25 Maintenance liquid for inkjet recording, ink set for inkjet recording, image forming method, and maintenance method

Publications (1)

Publication Number Publication Date
WO2013180074A1 true WO2013180074A1 (en) 2013-12-05

Family

ID=49673268

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/064670 WO2013180074A1 (en) 2012-05-29 2013-05-27 Maintenance fluid for inkjet recording, ink set for inkjet recording, image forming method, and maintenance method

Country Status (5)

Country Link
US (1) US9133359B2 (en)
EP (1) EP2857204B1 (en)
JP (1) JP5823613B2 (en)
CN (1) CN104349901B (en)
WO (1) WO2013180074A1 (en)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018087290A (en) * 2016-11-29 2018-06-07 京セラドキュメントソリューションズ株式会社 Water-based cleaning liquid for inkjet recording device, and cleaning method thereof
JP2018104637A (en) * 2016-12-28 2018-07-05 花王株式会社 Cleaning fluid for water-based ink
WO2018181058A1 (en) 2017-03-31 2018-10-04 富士フイルム株式会社 Aqueous ink composition, ink set, image forming method, and resin fine particles for inks
JP2018202760A (en) * 2017-06-06 2018-12-27 京セラドキュメントソリューションズ株式会社 Ink jet recording device and image formation method
JP2019064087A (en) * 2017-09-29 2019-04-25 セイコーエプソン株式会社 Recording method and recording device
WO2019181840A1 (en) 2018-03-23 2019-09-26 富士フイルム株式会社 Aqueous ink composition, ink set, and image forming method
WO2020179301A1 (en) 2019-03-06 2020-09-10 富士フイルム株式会社 Ink set, and image recording method
WO2020202774A1 (en) 2019-03-29 2020-10-08 富士フイルム株式会社 Inkjet ink for infrared absorbent image formation, method for infrared absorbent image formation, and recording material
JP2020189962A (en) * 2019-05-15 2020-11-26 株式会社パイロットコーポレーション Cleaning fluid for writing instruments and cleaning fluid package for writing instruments storing the same
WO2021084960A1 (en) 2019-10-29 2021-05-06 富士フイルム株式会社 Image recording product and production method therefor
WO2021140772A1 (en) 2020-01-10 2021-07-15 富士フイルム株式会社 Image recording method
WO2021171876A1 (en) 2020-02-28 2021-09-02 富士フイルム株式会社 Ink set and image recording method
WO2021171875A1 (en) 2020-02-28 2021-09-02 富士フイルム株式会社 Ink composition, ink set, and image recording method
WO2021221069A1 (en) 2020-04-27 2021-11-04 富士フイルム株式会社 Image recording method
WO2021229975A1 (en) 2020-05-11 2021-11-18 富士フイルム株式会社 Ink set, and method for recording image
WO2022065321A1 (en) * 2020-09-24 2022-03-31 日本化薬株式会社 Cleaning liquid for inkjet printer, cleaning method and storage method for inkjet printer, and liquid set
WO2022070848A1 (en) 2020-09-29 2022-04-07 富士フイルム株式会社 Inkjet yellow ink, image recording method, and image recorded matter
WO2022097503A1 (en) 2020-11-06 2022-05-12 富士フイルム株式会社 Ink set for permeable substrates, and image recording method
WO2022168833A1 (en) 2021-02-03 2022-08-11 富士フイルム株式会社 Inkjet ink set for impermeable substrate, image recording method, image recorded matter, laminate, and method for manufacturing laminate
WO2022168738A1 (en) 2021-02-04 2022-08-11 富士フイルム株式会社 Ink set and image recording method
WO2022190722A1 (en) 2021-03-09 2022-09-15 富士フイルム株式会社 Image recording method, image recorded material and inkset, and laminate and manufacturing method thereof
WO2022239625A1 (en) 2021-05-14 2022-11-17 富士フイルム株式会社 Ink-jet ink, ink set, and image-recording method
WO2023047785A1 (en) 2021-09-27 2023-03-30 富士フイルム株式会社 Ink-jet recording method and method for producing laminate
WO2023090046A1 (en) 2021-11-16 2023-05-25 富士フイルム株式会社 Inkjet ink and image-recording method
WO2023095710A1 (en) 2021-11-25 2023-06-01 富士フイルム株式会社 Inkjet recording method
EP4344893A1 (en) 2022-09-28 2024-04-03 FUJIFILM Corporation Image recording method

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10723142B2 (en) 2016-11-08 2020-07-28 Ricoh Company, Ltd. Image forming method, image forming apparatus, and method for manufacturing printed matter
CN109754260B (en) * 2017-11-01 2024-03-05 杭州沃朴物联科技有限公司 Anti-counterfeiting system based on vibration information characteristics and two-dimension code identification
EP3933020B1 (en) * 2019-02-26 2023-09-27 Nippon Kayaku Kabushiki Kaisha Use of a cleaning solution and inkjet printer cleaning method
JP7463836B2 (en) * 2020-05-14 2024-04-09 京セラドキュメントソリューションズ株式会社 Ink set and inkjet recording device
CN112277472A (en) * 2020-10-25 2021-01-29 郑州奥诚电子科技有限公司 Maintenance wiping method for nozzle of ink-jet printer and maintenance wiping wet tissue
JP6918263B1 (en) * 2021-03-23 2021-08-11 サカタインクス株式会社 Cleaning liquid, ink set, and cleaning method

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5459936A (en) 1977-10-03 1979-05-15 Canon Inc Recording method and device therefor
JP2001162692A (en) 1999-12-07 2001-06-19 Sekisui Chem Co Ltd Method for manufacturing lightweight composite panel and manufacturing device therefor
JP2001181549A (en) 1999-12-22 2001-07-03 Fuji Photo Film Co Ltd Dispersion of colored fine particle, ink for ink jet and ink jet printing process
JP2001247787A (en) 2000-03-07 2001-09-11 Fuji Photo Film Co Ltd Coloring fine-particle dispersoid, ink-jet ink, and ink jet recording method
JP2002088294A (en) 2000-09-19 2002-03-27 Fuji Photo Film Co Ltd Colored fine particle dispersion and ink for ink jet recording, made by using it
JP2005146224A (en) 2003-11-19 2005-06-09 Ricoh Co Ltd Cleaning liquid for inkjet-recording device and method for cleaning by using the same
JP2007100071A (en) 2005-09-07 2007-04-19 Fujifilm Corp Ink set and method and apparatus for recording image
JP2007217671A (en) * 2006-01-18 2007-08-30 Ricoh Co Ltd Recording ink, as well as, ink media set, ink cartridge, ink recorded matter, inkjet recording apparatus, and inkjet recording method
JP2010058374A (en) * 2008-09-03 2010-03-18 Fujifilm Corp Ink set for inkjet recording and inkjet recording method
JP2010155905A (en) 2008-12-26 2010-07-15 Fujifilm Corp Ink set and method for maintenance
JP2010188661A (en) 2009-02-19 2010-09-02 Fujifilm Corp Ink set for inkjet recording, and inkjet image recording method
JP2010241127A (en) 2009-03-19 2010-10-28 Fujifilm Corp Inkjet recording apparatus
JP2011046908A (en) 2009-07-30 2011-03-10 Fujifilm Corp Ink composition for inkjet, ink set, and method for forming image
JP2011063777A (en) 2009-09-18 2011-03-31 Fujifilm Corp Maintenance liquid, ink set and maintenance method
JP2011073295A (en) 2009-09-30 2011-04-14 Fujifilm Corp Head cleaning device and image recorder
JP2011073339A (en) 2009-09-30 2011-04-14 Fujifilm Corp Head cleaning device and image recorder
JP2011140556A (en) 2010-01-07 2011-07-21 Ricoh Co Ltd Inkjet device-cleaning solution and method of cleaning inkjet recording device
JP2012122537A (en) 2010-12-08 2012-06-28 Mitsubishi Heavy Ind Ltd Bearing damper

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4649823B2 (en) * 2003-06-18 2011-03-16 セイコーエプソン株式会社 Maintenance liquid for inkjet recording
CN1651247A (en) * 2005-02-01 2005-08-10 黎烈进 Method of cleaning printing machine head
US7686417B2 (en) * 2005-10-31 2010-03-30 Seiko Epson Corporation Maintenance liquid for ink jet recording
CN101096479A (en) * 2006-01-18 2008-01-02 株式会社理光 Recording ink as well as ink media set, ink cartridge, ink recorded matter, inkjet recording apparatus and inkjet recording method
KR20080104509A (en) * 2007-05-28 2008-12-03 삼성전자주식회사 Ink jet head cleaning apparatus and ink jet image forming apparatus having the same
JP5377197B2 (en) * 2009-09-28 2013-12-25 富士フイルム株式会社 Image forming method
CN101982316B (en) * 2010-08-20 2012-02-08 北京联创佳艺影像新材料技术有限公司 Method and special cleaning solutions for cleaning thermal-bubble ink-jet printer jet head

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5459936A (en) 1977-10-03 1979-05-15 Canon Inc Recording method and device therefor
JP2001162692A (en) 1999-12-07 2001-06-19 Sekisui Chem Co Ltd Method for manufacturing lightweight composite panel and manufacturing device therefor
JP2001181549A (en) 1999-12-22 2001-07-03 Fuji Photo Film Co Ltd Dispersion of colored fine particle, ink for ink jet and ink jet printing process
JP2001247787A (en) 2000-03-07 2001-09-11 Fuji Photo Film Co Ltd Coloring fine-particle dispersoid, ink-jet ink, and ink jet recording method
JP2002088294A (en) 2000-09-19 2002-03-27 Fuji Photo Film Co Ltd Colored fine particle dispersion and ink for ink jet recording, made by using it
JP2005146224A (en) 2003-11-19 2005-06-09 Ricoh Co Ltd Cleaning liquid for inkjet-recording device and method for cleaning by using the same
JP2007100071A (en) 2005-09-07 2007-04-19 Fujifilm Corp Ink set and method and apparatus for recording image
JP2007217671A (en) * 2006-01-18 2007-08-30 Ricoh Co Ltd Recording ink, as well as, ink media set, ink cartridge, ink recorded matter, inkjet recording apparatus, and inkjet recording method
JP2010058374A (en) * 2008-09-03 2010-03-18 Fujifilm Corp Ink set for inkjet recording and inkjet recording method
JP2010155905A (en) 2008-12-26 2010-07-15 Fujifilm Corp Ink set and method for maintenance
JP2010188661A (en) 2009-02-19 2010-09-02 Fujifilm Corp Ink set for inkjet recording, and inkjet image recording method
JP2010241127A (en) 2009-03-19 2010-10-28 Fujifilm Corp Inkjet recording apparatus
JP2011046908A (en) 2009-07-30 2011-03-10 Fujifilm Corp Ink composition for inkjet, ink set, and method for forming image
JP2011063777A (en) 2009-09-18 2011-03-31 Fujifilm Corp Maintenance liquid, ink set and maintenance method
JP2011073295A (en) 2009-09-30 2011-04-14 Fujifilm Corp Head cleaning device and image recorder
JP2011073339A (en) 2009-09-30 2011-04-14 Fujifilm Corp Head cleaning device and image recorder
JP2011140556A (en) 2010-01-07 2011-07-21 Ricoh Co Ltd Inkjet device-cleaning solution and method of cleaning inkjet recording device
JP2012122537A (en) 2010-12-08 2012-06-28 Mitsubishi Heavy Ind Ltd Bearing damper

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"AUTOMATIC SURFACE TENSIOMETER CBVP-Z", KYOWA INTERFACE SCIENCE CO. LTD.
R. F. FEDORS, POLYMER ENGINEERING SCIENCE, vol. 14, 1967, pages 147 - 154
See also references of EP2857204A4
TAKAYUKI OHTU; MASAETU KINOSHITA: "Kobunshi Gosei no Jikkenho", 1972, KAGAKU-DOJIN PUBLISHING COMPANY INC., pages: 124 - 154
TEIJI TSURUTA: "Kobunshi Gosei Hoho", 1971, NIKKAN KOGYO SHIMBUN, LTD.

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018087290A (en) * 2016-11-29 2018-06-07 京セラドキュメントソリューションズ株式会社 Water-based cleaning liquid for inkjet recording device, and cleaning method thereof
US10981385B2 (en) 2016-12-28 2021-04-20 Kao Corporation Cleaning liquid for aqueous ink
JP2018104637A (en) * 2016-12-28 2018-07-05 花王株式会社 Cleaning fluid for water-based ink
WO2018181058A1 (en) 2017-03-31 2018-10-04 富士フイルム株式会社 Aqueous ink composition, ink set, image forming method, and resin fine particles for inks
JP2018202760A (en) * 2017-06-06 2018-12-27 京セラドキュメントソリューションズ株式会社 Ink jet recording device and image formation method
JP2019064087A (en) * 2017-09-29 2019-04-25 セイコーエプソン株式会社 Recording method and recording device
WO2019181840A1 (en) 2018-03-23 2019-09-26 富士フイルム株式会社 Aqueous ink composition, ink set, and image forming method
WO2020179301A1 (en) 2019-03-06 2020-09-10 富士フイルム株式会社 Ink set, and image recording method
WO2020202774A1 (en) 2019-03-29 2020-10-08 富士フイルム株式会社 Inkjet ink for infrared absorbent image formation, method for infrared absorbent image formation, and recording material
JP2020189962A (en) * 2019-05-15 2020-11-26 株式会社パイロットコーポレーション Cleaning fluid for writing instruments and cleaning fluid package for writing instruments storing the same
JP7419129B2 (en) 2019-05-15 2024-01-22 株式会社パイロットコーポレーション Writing instrument cleaning liquid and writing instrument cleaning liquid package containing the same
WO2021084960A1 (en) 2019-10-29 2021-05-06 富士フイルム株式会社 Image recording product and production method therefor
WO2021140772A1 (en) 2020-01-10 2021-07-15 富士フイルム株式会社 Image recording method
WO2021171876A1 (en) 2020-02-28 2021-09-02 富士フイルム株式会社 Ink set and image recording method
WO2021171875A1 (en) 2020-02-28 2021-09-02 富士フイルム株式会社 Ink composition, ink set, and image recording method
WO2021221069A1 (en) 2020-04-27 2021-11-04 富士フイルム株式会社 Image recording method
WO2021229975A1 (en) 2020-05-11 2021-11-18 富士フイルム株式会社 Ink set, and method for recording image
WO2022065321A1 (en) * 2020-09-24 2022-03-31 日本化薬株式会社 Cleaning liquid for inkjet printer, cleaning method and storage method for inkjet printer, and liquid set
WO2022070848A1 (en) 2020-09-29 2022-04-07 富士フイルム株式会社 Inkjet yellow ink, image recording method, and image recorded matter
WO2022097503A1 (en) 2020-11-06 2022-05-12 富士フイルム株式会社 Ink set for permeable substrates, and image recording method
WO2022168833A1 (en) 2021-02-03 2022-08-11 富士フイルム株式会社 Inkjet ink set for impermeable substrate, image recording method, image recorded matter, laminate, and method for manufacturing laminate
WO2022168738A1 (en) 2021-02-04 2022-08-11 富士フイルム株式会社 Ink set and image recording method
WO2022190722A1 (en) 2021-03-09 2022-09-15 富士フイルム株式会社 Image recording method, image recorded material and inkset, and laminate and manufacturing method thereof
WO2022239625A1 (en) 2021-05-14 2022-11-17 富士フイルム株式会社 Ink-jet ink, ink set, and image-recording method
WO2023047785A1 (en) 2021-09-27 2023-03-30 富士フイルム株式会社 Ink-jet recording method and method for producing laminate
WO2023090046A1 (en) 2021-11-16 2023-05-25 富士フイルム株式会社 Inkjet ink and image-recording method
WO2023095710A1 (en) 2021-11-25 2023-06-01 富士フイルム株式会社 Inkjet recording method
EP4344893A1 (en) 2022-09-28 2024-04-03 FUJIFILM Corporation Image recording method

Also Published As

Publication number Publication date
US9133359B2 (en) 2015-09-15
JPWO2013180074A1 (en) 2016-01-21
CN104349901A (en) 2015-02-11
EP2857204B1 (en) 2016-11-09
CN104349901B (en) 2016-08-24
US20150077465A1 (en) 2015-03-19
EP2857204A1 (en) 2015-04-08
JP5823613B2 (en) 2015-11-25
EP2857204A4 (en) 2015-12-16

Similar Documents

Publication Publication Date Title
JP5823613B2 (en) Inkjet recording maintenance liquid, inkjet recording ink set, image forming method, and maintenance method
CN107001835B (en) Water-based ink
JP4587069B2 (en) Water-based ink composition
US9309422B2 (en) Ink set for inkjet recording and image forming method
JP5523772B2 (en) Ink jet ink composition, ink set, and image forming method
JP5538966B2 (en) Ink composition, ink set, and image forming method
JP5819206B2 (en) Inkjet recording maintenance liquid, inkjet recording ink set, image forming method, and maintenance method
JP2011068085A (en) Maintenance liquid for inkjet recording, ink set, and image forming method
JP2013064074A (en) Ink composition, ink set and image forming method
JP5738693B2 (en) Inkjet recording maintenance liquid, inkjet recording ink set, and image forming method
US20110234692A1 (en) Maintenance liquid for ink jet recording, method of manufacturing maintenance liquid for ink jet recording, ink set for ink jet recording, and image forming method
EP2366745B1 (en) Ink composition, ink set and inkjet image forming method
JP2013146952A (en) Maintenance liquid for inkjet recording, ink set for inkjet recording, image forming method, and maintenance method
JP2013176960A (en) Maintenance liquid for ink jet recording, ink set for ink jet recording, image forming method, and maintenance method
JP5819205B2 (en) Inkjet recording maintenance liquid, inkjet recording ink set, image forming method, and maintenance method
JP5258535B2 (en) Maintenance liquid for ink jet recording, ink set, and maintenance method
JP2005154549A (en) Water-based ink composition and inkjet printing method using the same, and printed matter
JP2012180425A (en) Ink composition, ink set, and image forming method
JP2015021084A (en) Ink jet recording ink set and image forming method
JP2006257361A (en) Water-based ink composition
JP5523697B2 (en) Ink set and maintenance method
JP2006274030A (en) Water-based pigment ink and method for ink-jet recording and record using the same
JP2005232360A (en) Water-based ink composition, inkjet recording method using it, and recorded matter
JP5714360B2 (en) Ink composition, ink set, and image forming method
JPWO2020179301A1 (en) Ink set and image recording method

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13796414

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014518435

Country of ref document: JP

Kind code of ref document: A

REEP Request for entry into the european phase

Ref document number: 2013796414

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2013796414

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE